WO2025117570A1

WO2025117570A1 - Use of ethylene inhibitors and 1-aminocyclopropane-l- carboxylic acid for improved fruit maturation

Info

Publication number: WO2025117570A1
Application number: PCT/US2024/057503
Authority: WO
Inventors: Sherif M. SHERIF
Original assignee: Virginia Tech Intellectual Properties Inc
Current assignee: Virginia Tech Intellectual Properties Inc
Priority date: 2023-11-30
Filing date: 2024-11-26
Publication date: 2025-06-05
Anticipated expiration: 2026-05-30

Abstract

Described herein are formulations and methods for enhancing one or more characteristics of a fruit and/or reducing one or more negative effects of an ethylene inhibitor on a plant or component thereof, such as a fruit plant or fruit produced therefrom.

Description

USE OF ETHYLENE INHIBITORS AND 1-AMINOCYCLOPROPANE-l- CARBOXYLIC ACID FOR IMPROVED FRUIT MATURATION

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Patent Application No. 63/604,279, filed on November 30, 2023, and U.S. Provisional Patent Application No. 63/669,380, filed on July 10, 2024, the contents of which are incorporated by reference herein in their entireties.

TECHNICAL FIELD

[0002] The subject matter disclosed herein is generally directed to agricultural biotechnology, and more specifically to the application of plant growth regulators (PGRs) and fruit maturation management.

BACKGROUND

[0003] The coloration of fruits and vegetables is a critical indicator of maturation and ripening and is primarily influenced by anthocyanin levels. Ethylene is a natural ripening hormone in fruits and vegetables. For example, ethylene enhances the red pigmentation of apples by regulating anthocyanin biosynthesis but can cause premature fruit dropping. While ethylene inhibitors like aminoethoxy vinylgly cine (AVG) are used to reduce pre-harvest fruit drop, they often result in undesirable diminished fruit coloration. As such, there exists a need for approaches to mitigating or eliminating deleterious effects of ethylene inhibitors, particularly in fruit and vegetable cultivation.

[0004] Citation or identification of any document in this application is not an admission that such a document is available as prior art to the present invention.

SUMMARY

[0005] In some aspects, the techniques described herein relate to a fruit maturation formulation including: an amount of an ethylene inhibitor; and an amount of 1 -amino- 1- cyclopropanecarboxylic acid (ACC), a salt thereof, hydrate thereof, or a polymorph thereof.

[0006] In some aspects, the techniques described herein relate to a formulation, wherein the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to reduce a negative effect of the ethylene inhibitor on a characteristic of a fruit as compared to a suitable control. [0007] In some aspects, the techniques described herein relate to a formulation, wherein the characteristic is fruit color.

[0008] In some aspects, the techniques described herein relate to a formulation, wherein the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to enhance fruit color as compared to a fruit exposed to an ethylene inhibitor alone.

[0009] In some aspects, the techniques described herein relate to a formulation, wherein the amount of the ethylene inhibitor is effective to reduce pre-harvest fruit drop in a plant or tree.

[0010] In some aspects, the techniques described herein relate to a formulation, wherein the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof does not significantly impact the reduction in pre-harvest fruit drop in the plant or tree.

[0011] In some aspects, the techniques described herein relate to a formulation, wherein the amount of the ethylene inhibitor ranges from about 100 g to about 1500 g, such as about 126 g to about 1261g; wherein the amount of the ethylene inhibitor ranges from about 100 mL to about 1500 mL, such as about 126 mL to about 1261 mL; wherein the amount of the ethylene inhibitor ranges from about 50 ppm to about 500 ppm; or wherein the amount of the ethylene inhibitor is present at about 15 percent wt/wt or v/v of the formulation. In some embodiments, these amounts are based on per 100 gallons of water per acre.

[0012] In some aspects, the techniques described herein relate to a formulation, wherein the amount of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof ranges from about 350 g to about 4,000 g, such as about 378 g, to about 3784 g; wherein the amount of the ACC ranges from about 350 mL to about 4,000 mL, such as about 378 mL to about 3785 mL; wherein the amount of the ACC ranges from about 100 ppm to 1000 ppm; or wherein the amount of ACC is present at about 10 percent wt/wt or v/v of the formulation. In some embodiments, these amounts are based on per 100 gallons of water per acre.

[0013] In some aspects, the techniques described herein relate to a formulation, wherein the ratio of the amount of the ethylene inhibitor to the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof is about 0.2-1.0 to 1.0.

[0014] In some aspects, the techniques described herein relate to a formulation, wherein the ethylene inhibitor is aminoethoxyvinylglycine (AVG) (including, but not limited to, 2- aminoethoxyvinyl glycine, N-acetyl aminoethoxyvinylglycine, a compound described in Mexico Patent Application Publication MXPA99002753A, U.S. Pat. No. 5,801,119, and AVG hydrochloride (AVG HC1)), methoxyvinylglycine (MVG), silver or silver ions, silver thiosulphate, cobalt or cobalt ions, a cyclopropane (e.g., 1 -methylcyclopropene (MCP) or any other set forth in U.S. Patent No. 5,518,988), a pyrazinamide or a derivative thereof (such as any one described in Sun et al., Nat. Commun., 2017, 8: 15758), 2,5-norbomadiene (2,5-NBD), diazocyclopentadiene (DACP), aminooxyacetic acid, or a compound or composition as set forth in Japanese Patent Publication JP4963568B2, or any combination thereof.

[0015] In some aspects, the techniques described herein relate to a formulation, wherein the ethylene inhibitor is AVG or MCP.

[0016] In some aspects, the techniques described herein relate to a formulation, wherein the formulation is a concentrate.

[0017] In some aspects, the techniques described herein relate to a formulation, wherein the formulation is ready to use.

[0018] In some aspects, the techniques described herein relate to a formulation, wherein the formulation is a solid or a liquid.

[0019] In some aspects, the techniques described herein relate to a formulation, wherein the fruit is a pome fruit.

[0020] In some aspects, the techniques described herein relate to a formulation, wherein the fruit is an apple, peach, pear, or nectarine.

[0021] In some aspects, the techniques described herein relate to a method of improving fruit maturation in a plant or tree, the method including: applying to a plant an amount of an ethylene inhibitor; and applying to a plant an amount of 1 -amino- 1 -cyclopropanecarboxylic acid (ACC), a salt thereof, hydrate thereof, or a polymorph thereof.

[0022] In some aspects, the techniques described herein relate to a method, wherein the amount of the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof are applied simultaneously.

[0023] In some aspects, the techniques described herein relate to a method, wherein the amount of the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof are contained in the same formulation.

[0024] In some aspects, the techniques described herein relate to a method, wherein the formulation is a formulation of the present disclosure.

[0025] In some aspects, the techniques described herein relate to a method, wherein the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof are contained in separate formulations.

[0026] In some aspects, the techniques described herein relate to a method, wherein the amount of the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, are applied at separate times. [0027] In some aspects, the techniques described herein relate to a method, wherein the amount of the ethylene inhibitor ranges from about 100 g to about 1500 g, such as about 126 g to about 1261g; wherein the amount of the ethylene inhibitor ranges from about 100 mL to about 1500 mL, such as about 126 mL to about 1261 mL; wherein the amount of the ethylene inhibitor ranges from about 50 ppm to about 500 ppm; or wherein the amount of the ethylene inhibitor is present at about 15 percent w/w or v/v of the formulation. In some embodiments, these amounts are based on per 100 gallons of water per acre.

[0028] In some aspects, the techniques described herein relate to a method, wherein the amount of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof ranges from about 350 g to about 4,000 g, such as about 378 g, to about 3784 g; wherein the amount of the ACC ranges from about 350 mL to about 4,000 mL, such as about 378 mL to about 3785 mL; wherein the amount of the ACC ranges from about 100 ppm to 1000 ppm; or wherein the amount of ACC is present at about 10 percent wt/wt or v/v of the formulation. In some embodiments, these amounts are based on per 100 gallons of water per acre.

[0029] In some aspects, the techniques described herein relate to a method, wherein the ratio of the amount of the ethylene inhibitor to the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof is about 0.2-1.0 to 1.0.

[0030] In some aspects, the techniques described herein relate to a method, wherein the ethylene inhibitor is aminoethoxyvinylglycine (AVG) (including, but not limited to, 2- aminoethoxyvinyl glycine, N-acetyl aminoethoxyvinylglycine, a compound described in Mexico Patent Application Publication MXPA99002753A, U.S. Pat. No. 5,801,119, and AVG hydrochloride (AVG HC1)), methoxyvinylglycine (MVG), silver or silver ions, silver thiosulphate, cobalt or cobalt ions, a cyclopropane (e.g., 1 -methylcyclopropene (MCP) or any other set forth in U.S. Patent No. 5,518,988), a pyrazinamide or a derivative thereof (such as any one described in Sun et al., Nat. Commun., 2017, 8: 15758), 2,5-norbomadiene (2,5-NBD), diazocyclopentadiene (DACP), aminooxyacetic acid, or a compound or composition as set forth in Japanese Patent Publication JP4963568B2, or any combination thereof.

[0031] In some aspects, the techniques described herein relate to a method, wherein the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to reduce a negative effect of the ethylene inhibitor on a characteristic of a fruit as compared to a suitable control.

[0032] In some aspects, the techniques described herein relate to a method, wherein the characteristic is fruit color. [0033] In some aspects, the techniques described herein relate to a method, wherein the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to enhance fruit color as compared to a fruit exposed to an ethylene inhibitor alone.

[0034] In some aspects, the techniques described herein relate to a method, wherein the amount of the ethylene inhibitor is effective to reduce pre-harvest fruit drop in a plant or tree.

[0035] In some aspects, the techniques described herein relate to a method, wherein the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof does not significantly impact the reduction in pre-harvest fruit drop in the plant or tree.

[0036] In some aspects, the techniques described herein relate to a method, wherein the fruit or plant or tree is a pome fruit, plant, or tree.

[0037] In some aspects, the techniques described herein relate to a method, wherein the fruit or plant, or tree is an apple, peach, pear, or nectarine fruit, plant, or tree.

[0038] These and other aspects, objects, features, and advantages of the example embodiments will become apparent to those having ordinary skill in the art upon consideration of the following detailed description of example embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

[0039] An understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention may be utilized, and the accompanying drawings of which:

[0040] FIG. 1 shows the influence of Accede® Plant Growth Regulator and ReTain® Plant Growth Regulator mixture on enhancing fruit in 'Honeycrisp' Apples at standard harvest time and two-weeks post-harvest.

[0041] FIG. 2 shows the influence of Accede® Plant Growth Regulator on enhancing fruit coloration in 'Gala' Apples at standard harvest time and two-weeks post-harvest.

[0042] FIG. 3 shows the influence of Accede® Plant Growth Regulator and ReTain® Plant Growth Regulator mixture on enhancing fruit in 'Honeycrisp' Apples at standard harvest time and two-weeks post-harvest in 2024.

[0043] FIG. 4 shows the influence of Accede® Plant Growth Regulator on enhancing fruit coloration in 'Gala' Apples at standard harvest time in 2024.

[0044] The figures herein are for illustrative purposes only and are not necessarily drawn to scale. DETAILED DESCRIPTION OF THE EXAMPLE EMBODIMENTS

[0045] Before the present disclosure is described in greater detail, it is to be understood that this disclosure is not limited to particular embodiments described, and as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0046] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described.

[0047] All publications and patents cited in this specification are cited to disclose and describe the methods and/or materials in connection with which the publications are cited. All such publications and patents are herein incorporated by references as if each individual publication or patent were specifically and individually indicated to be incorporated by reference. Such incorporation by reference is expressly limited to the methods and/or materials described in the cited publications and patents and does not extend to any lexicographical definitions from the cited publications and patents. Any lexicographical definition in the publications and patents cited that is not also expressly repeated in the instant application should not be treated as such and should not be read as defining any terms appearing in the accompanying claims. The citation of any publication is for its disclosure prior to the filing date and should not be construed as an admission that the present disclosure is not entitled to antedate such publication by virtue of prior disclosure. Further, the dates of publication provided could be different from the actual publication dates that may need to be independently confirmed.

[0048] As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible.

[0049] Where a range is expressed, a further aspect includes from the one particular value and/or to the other particular value. Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure. For example, where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g. the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y’. The range can also be expressed as an upper limit, e.g. ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of Tess than x’, less than y’, and Tess than z’ . Likewise, the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘greater than x’, greater than y’, and ‘greater than z’. In addition, the phrase “about ‘x’ to ‘y’”, where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about ‘y’”.

[0050] It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further aspect. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0051] It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “about 0.1% to 5%” should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and the subranges (e.g., about 0.5% to about 1.1%; about 5% to about 2.4%; about 0.5% to about 3.2%, and about 0.5% to about 4.4%, and other possible sub-ranges) within the indicated range. General Definitions

[0052] Unless defined otherwise, technical, and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. Definitions of common terms and techniques in chemistry and organic chemistry can be found in Smith. Organic Synthesis, published by Academic Press. 2016; Tinoco et al. Physical Chemistry, 5^th edition (2013) published by Pearson; Brown et al., Chemistry, The Central Science 14^th ed. (2017), published by Pearson, Clayden et al., Organic Chemistry, 2^nd ed. 2012, published by Oxford University Press; Carey and Sunberg, Advanced Organic Chemistry, Part A: Structure and Mechanisms, 5^th ed. 2008, published by Springer; Carey and Sunberg, Advanced Organic Chemistry, Part B: Reactions and Synthesis, 5^th ed. 2010, published by Springer, and Vollhardt and Schore, Organic Chemistry, Structure and Function; 8^th ed., 2018, published by W.H. Freeman.

[0053] Definitions of common terms and techniques in fruit horticulture can be found in Modem Fruit Science, Childers et al., 1995, published by Horticultural Publications, Gainesville, FL; Fruit Culture, Its Science and Art, 1988, by K. Ryugo. John Wiley & Sons, Wiley-Interscience, New York, NY; Genetics and Breeding of Fruit Trees, Eds. Zhang and Xing, 2023, published by MDPI Books, Basel, Switzerland; Sittig’s Handbook of Pesticides and Agriculture Chemicals 2^nd ed., 2014, R. P. Pohanish, published by Elsevier, Amsterdam, Netherlands; and Fruit Production: Horticultural Practices, 2019, P. Hunter, published by Syrawood Publishing House, New York, NY.

[0054] As used herein, the singular forms “a”, “an”, and “the” include both singular and plural referents unless the context clearly dictates otherwise.

[0055] As used herein, "about," "approximately," “substantially,” and the like, when used in connection with a measurable variable such as a parameter, an amount, a temporal duration, and the like, are meant to encompass variations of and from the specified value including those within experimental error (which can be determined by e.g. given data set, art accepted standard, and/or with e.g. a given confidence interval (e.g. 90%, 95%, or more confidence interval from the mean), such as variations of +/-10% or less, +/-5% or less, +/-1% or less, and +/-0.1% or less of and from the specified value, insofar such variations are appropriate to perform in the disclosed invention. As used herein, the terms “about,” “approximate,” “at or about,” and “substantially” can mean that the amount or value in question can be the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art such that equivalent results or effects are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about,” “approximate,” or “at or about” whether or not expressly stated to be such. It is understood that where “about,” “approximate,” or “at or about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0056] The term “optional” or “optionally” means that the subsequent described event, circumstance or substituent may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0057] As used herein, “prior to harvest,” “before harvest,” and “preharvest” all refer to a time before the most mature fruits are harvested from plant or tree.

[0058] The recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within the respective ranges, as well as the recited endpoints.

[0059] Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment(s). Reference throughout this specification to “one embodiment”, “an embodiment,” “an example embodiment,” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment,” “in an embodiment,” or “an example embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention. For example, in the appended claims, any of the claimed embodiments can be used in any combination.

[0060] All publications, published patent documents, and patent applications cited herein are hereby incorporated by reference to the same extent as though each individual publication, published patent document, or patent application was specifically and individually indicated as being incorporated by reference.

OVERVIEW

[0061] The coloration of fruits and vegetables is a critical indicator of maturation and ripening and is primarily influenced by anthocyanin levels. Ethylene is a natural ripening hormone in fruits and vegetables. For example, ethylene enhances the red pigmentation of apples by regulating anthocyanin biosynthesis but can cause premature fruit dropping. While ethylene inhibitors like 2-aminoethoxyvinyl glycine (AVG) are used to reduce pre-harvest fruit drop, they often result in undesirable diminished fruit coloration. Further, Applicant shows that ACC, when used alone may improve color but leads to increased fruit drop in early-maturing cultivars when used close to the harvest window.

[0062] With at least these deficiencies in mind, embodiments disclosed herein describe a method of mitigating one or more deleterious effects of an ethylene inhibitor by applying 1- aminocyclopropane-1 -carboxylic acid (ACC) to a crop in combination with an ethylene inhibitor. Also described herein are formulations comprising an amount of an ethylene inhibitor and an amount of an ACC. In some embodiments, the formulations can be used in a method for mitigating one or more deleterious effects of an ethylene inhibitor. As is demonstrated in at least the Working Examples herein, the present disclosure offers an improvement over current practices for fruit maturation management by providing growers with an effective strategy to manage pre-harvest fruit drop while limiting deleterious effect on fruit color quality due current pre-harvest drop management practices. The formulations and methods of the present disclosure can be especially advantageous when the harvest period for early-maturing cultivars is extended beyond the traditional window. Thus, the formulations and methods of the present disclosure can extend the harvesting window, allowing for greater flexibility and potentially higher yields of marketable fruit. Further, the formulations and methods of the present disclosure may not only enhance fruit quality and marketability but also increase profitability for growers.

[0063] Other compositions, methods, features, and advantages of the present disclosure will be or become apparent to one having ordinary skill in the art upon examination of the following drawings, detailed description, and examples. It is intended that all such additional compositions, compounds, methods, features, and advantages be included within this description, and be within the scope of the present disclosure. FORMULATIONS

[0064] Described herein are formulations comprising an amount of an ethylene inhibitor and/or an amount of ACC, also referred to generally as the active ingredient(s) in the context of the formulations described herein. In some embodiments, the formulation contains both an amount of an ethylene inhibitor and an amount of ACC. In some embodiments, the amount of ethylene inhibitor is effective to reduce or slow fruit ripening and/or reduce fruit drop. In some embodiments, the amount of ACC is effective to reduce or eliminate one or more negative side effects such as discoloration of the ethylene inhibitor. The formulations can be solid, liquid, or gas.

[0065] In some embodiments, the amount of the ethylene inhibitor ranges from about 100 g to about 1500 g, such as about 126 g to about 1261g; wherein the amount of the ethylene inhibitor ranges from about 100 mL to about 1500 mL, such as about 126 mL to about 1261 mL; wherein the amount of the ethylene inhibitor ranges from about 50 ppm to about 500 ppm; or wherein the amount of the ethylene inhibitor is present at about 15 percent wt/wt or v/v of the formulation. In some embodiments, the amount of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof ranges from about 350 g to about 4,000 g, such as about 378 g, to about 3784 g; wherein the amount of the ACC ranges from about 350 mL to about 4,000 mL, such as about 378 mL to about 3785 mL; wherein the amount of the ACC ranges from about 100 ppm to 1000 ppm; or wherein the amount of ACC is present at about 10 percent wt/wt or v/v of the formulation. In some embodiments, these amounts are based on per 100 gallons of water per acre.

[0066] In some embodiments, the formulation is a liquid formulation. In some embodiments, the liquid formulation is a ready to use formulation. In some embodiments, the liquid formulation is a concentrate, that prior to use, is diluted with water or another liquid to a working concentration for direct use.

[0067] In some embodiments, the formulation is a tablet. Tablet formulations are premeasured dosage delivery systems. In some embodiments, the tablet formulation is effervescent, which dissolve in water over a period of two to ten minutes depending upon the type and size of the tablet. In some embodiments, the table formulation delivers between 0.1- 1 gram of the active ingredient(s) per tablet.

[0068] In some embodiments, the formulation is a powder. In some embodiments, the powder is a soluble or wettable powder. A soluble powder formulation is one which, when mixed with water or other liquid, dissolves readily in water and forms a true solution. Once the solution is formed, no further mixing or agitation of the tank-mix is required. Mixing is a process of combining different materials, usually, but not necessarily, to a homogeneous state. Agitation aids the process of mixing and is a mechanical process involving rotating shafts of blades in the bottom of the spray tank. A wettable powder formulation is a dry, finely ground formulation. In this formulation, the active ingredient is combined with a finely ground dry carrier, usually a mineral clay, along with other ingredients, which will be known to those of skill in the art, that enhance the ability of the powder to be suspended in water. Upon mixing the wettable powder with water, a suspension is formed, which is then applied by a spray technique.

[0069] In some embodiments, the formulation is a liquid dispersible granular formulation. In some embodiments, the formulation is a water dispersible granular formulation. Water- dispersible granules are also known as wettable granules or dry flowables. This type of formulation is similar to a wettable powder, except that the active ingredient(s) is/are formulated as a dispersible granule. To prepare the water-dispersible granules for spray application, they are dispersed in water and form a suspension upon agitation. Many different water-dispersible granular formulations are known for agricultural chemicals. For example, EP 0 252 897 and U.S. Pat. No. 4,936,901 disclose encapsulated plant growth regulators in water dispersible granular formulations; and U.S. Pat. No. 5,622,658 discloses an extrudable composition for preparing water-dispersible granules. These can be adapted for forming the formulation of the present disclosure.

[0070] In some embodiments, the formulation is a water-soluble granular composition that includes at least 40% of the active ingredient(s) at least one binder, at least one disaccharide and at least one surfactant. In some embodiments, the water-soluble granular composition contains from about 40 to about 80 weight percent plant growth regulator, from about 0.1 to about 10 weight percent binder, from about 5 to about 95 weight percent disaccharide and from about 0.1 to about 10 weight percent surfactant. In some embodiments, the disaccharide is lactose monohydrate, the binder is polyvinylpyrrolidone, and the surfactant is a polyoxyethylene 20 monolaurate. Water soluble granules for delivery of growth regulators are described in e.g., U.S. Pat. Publication No. US 2003/0008949 and US 2022/0240512; and U.S. Pat. No. 6,984,609; which can be adapted for use with the ACC and/or ethylene inhibitor and formulations of the present disclosure.

[0071] The formulations can include other ingredients such as binders, surfactants, surface active agents, inert carriers, diluents, extenders, fillers, conditioners, excipients and/or the like. Binders can aid in binding, disintegration and solubilization of the formulation. Suitable binders that can be included in the formulation , include without limitation, a polyvinylpyrrolidone, alkylated vinyl pyrrolidone copolymers such as AGRIMER AL- 10 and AGRIMER AL-10LC; cross-linked polyvinylpyrrolidones such as AGRIMER AT and AGRIMER ATF; copolymers of vinyl acetate and vinylpyrrolidone such as AGRIMER VA-6 and AGRIMER VA-7; lignosulfonates and sodium or calcium salts thereof such as MARASPERSE, VANISPERSE, BORRESPERSE, NORLIG, POLYFON and KRAFTSPERSE; unsulfonated lignins such as INDULIN AT; clays such as HYDRITE RS, microcrystalline celluloses such as AVICEL PH and LATTICE NT; methyl cellulose ethers such as METHOCEL; ethyl cellulose polymers such as ETHOCEL; starch (natural or modified); gluten; silicates and sodium or calcium salts thereof; magnesium aluminum silicates such as VEEGUM F; natural or modified lecithins such as BEAKIN, CENTROMIX or YELKIN; sugar alcohols such as NEOSORB, SORBOGEM, MANOGEM and MALTISWEET and polyethylene glycols, a lignosulfonate among others. A presently preferred binder is polyvinylpyrrolidone such as AGRIMER 15, AGRIMER 30, AGRIMER 60, AGRIMER 90 and PLASDONE.

[0072] In some embodiments, the diluent is a disaccharide. Suitable disaccharides include sucrose, lactose and maltose, hydrolyzed starches such as maltodextrin and corn syrup solids, sugar alcohols such as sorbitol and mannitol and other sugars such as fructose and glucose among others. In some embodiments, the disaccharide is lactose monohydrate.

[0073] In some embodiments, the formulation includes one or more wetting agents. Suitable wetting agents include, without limitation, a non-ionic ethoxylated sorbitan, a polyoxyethylene glycol alkyl ether and an anionic dioctyl sulfosuccinate. Additional wetting agents suitable for use with the formulations of the present disclosure include, but are not limited to, non-ionic surfactants, such as ethoxylated sorbitans including the polysorbates in the Tween® series such as Tween® 20-24, 40, 60, 80 and the like (Tween is a registered trademark of and available from Croda Americas LLC), polyoxyethylene glycol alkyl ethers including the Brij® series such as Brij® 35, 78, 98, 700, 020, CIO, C2, C20, L4, L23, S20 and the like (Brij is a registered trademark of and available from Croda Americas LLC) and anionic surfactants such as, dioctyl sulfosuccinates including Aerosol® anionic surfactants such as 22, A-102, C-61, OT-75, OT-A, OT-B, and the like (Aerosol is a registered trademark of Cytec Technology Corp and available from Solvay). In some embodiments, the wetting agent is selected from the group of polyoxyethylene vegetable-based fatty ether derived from cetyl alcohol (Brij® 020), polysorbate 20 (Tween® 20) and dioctyl sulfosuccinate sodium salt (Aerosol® OT-B). [0074] Surfactants can be useful to include and can optionally function as a wetting agent, as well as a dispersing and granulating aid. Suitable surfactants include non-ionic surfactants, anionic surfactants and amphoteric surfactants. Non-ionic surfactants include ethoxylated sorbitan esters such as EMSORB, TWEEN, and T-MAZE; sorbitan fatty acid esters such as SPAN and ALKAMUL; sucrose and glucose esters and derivatives thereof such as MAZON, RHEOZAN and GLUCOPON; ethoxylated alcohols such as TRYCOL, BRIJ, ARMIX and PLURAFAC; ethoxylated alkylphenols such as IGEPAL, MACOL and TERGITOL; ethoxylated fatty amines such as TRYMEEN and ETHOMEEN; ethoxylated fatty acids such as EMEREST, ALKAMUL and TRYDET; ethoxylated fatty esters and oils such as ALKAMUL and ATLAS G; fatty acids such as ATLAS G-1556; glycerol esters such as MAZOL GMO; glycol esters such as GLYCOL SEG; lanolin-based derivatives such as AMERCHOL CAB; methyl esters such as OLEOCAL ME; monoglycerides and derivatives such as ETHOSPERSE G-26; propoxylated and ethoxylated fatty acids such as ANTAROX AA-60; block copolymers of ethylene oxide and propylene oxide such as PLURONIC or SURFONIC; silicone-based surfactants such as SIL WET, BREAKTHRU, an organosilicon surfactant (e.g., a polyalkyleneoxide modified heptamethyltrisiloxane and a polyether trisiloxane), and mixtures of organosilicon surfactant with non-ionic or ionic surfactants; polysaccharides, copolymers of acrylamide and acrylic acid; and acetylenic diol derivatives such as SURFYNOL 104 or tri styrylphenols such as SOPROPHOR among others. In some embodiments, the surfactant family is the ethoxylated sorbitan esters. Non-ionic surfactants such as polyoxyethylene (20) monolaurate (TWEEN 20 or POLYSORBATE 20) are presently most preferred. Suitable anionic surfactants include phosphate esters such as EMPHOS and RHODAFAC; sulfates and sulfonates of oils and fatty acids such as POLYSTEP; sulfates and sulfonates of ethoxylated alkylphenols such as TRITON X-301; sulfates of dodecyl and tridecylbenzenes such as CALMULSE; sulfonates of condensed naphthalenes such as VULTAMOL; sulfonates of naphthalene and alkyl naphthalene such as MOREWET and sulfuosuccinates and derivatives such as MONAWET, among others. In some embodiments, the Organosilicon surfactants suitable for use in the present formulation, include, but are not limited to polyalkyleneoxide modified heptamethyltrisiloxane (Silwet ECO spreader; Silwet is a registered trademarks of and available from Momentive Performance Chemicals) and a polyether trisiloxane including Break-Thru® S series polyether trisiloxanes such as S 200, S 233, S 240, S 279 and S 301. [0075] In some embodiments, the formulation includes one or more fillers. Suitable fillers include, without limitation, lactose, dextrose, sucrose, maltodextrin, a sugar alcohol or any combination thereof.

[0076] In some embodiments, the formulation includes one or more additional surfaceactive agents, stickers, spreader stickers, nematicides, systemic acquired resistance inducers, inert carriers, preservatives, humectants, dyes, U.V. (ultra-violet) protectants, buffers, flow agents, antifoams or other components which facilitate product handling and application.

[0077] Examples of inert carriers that can be included in the formulation include, without limitation, inorganic minerals such as kaolin, mica, gypsum, fertilizer, carbonates, sulfates, or phosphates; organic materials such as sugar, starches or cyclodextrins; or botanical materials such as wood products, cork, powdered corn cobs, rice hulls, peanut hulls and walnut shells. In some embodiments, an antifoam is polydimethylsiloxane. In some embodiments, the carrier is sodium aluminosilicate.

[0078] In some embodiments, the formulation of the present disclosure can include or be used in combination with other essential biologicals or beneficial microorganisms or active ingredients, such as herbicides, anti-microbials, fungicides, insecticides, nematicides, biological pesticides such as microbial pesticides, biochemical pesticides (semiochemicals, hormones or natural plant regulators), plant produced pesticides (botanicals) or plant nutrients. [0079] In some embodiments, the formulation further includes one or more pH adjustors. pH adjustors suitable for use in the present invention include, but are not limited to, citric acid, malic acid and the like. pH adjustors may be present in compositions of the present invention at a concentration necessary to adjust the pH to a value from about 4 to about 6 and more preferably from about 4 to about 5.

[0080] In some embodiments, the formulation includes an amount of calcium chloride. Calcium chloride can be present in the formulation at a concentration from about 1% to about 50% w/w, more preferably from about 2% to about 30% w/w, even more preferably from about 5% to about 20% w/w and most preferably at about 5%, about 10% or about 20% w/w.

[0081] In some embodiments, the formulation is formulated as an active mixture, which may include finely divided dry diluents, extenders, fillers, conditioners, and excipients, including various clays, diatomaceous earth, talc and the like and mixtures thereof. In some embodiments, the formulation includes a free flow agent. Free flow agents suitable for use in the present disclosure include, but are not limited to, silicon dioxide and precipitated sodium alumino silicate. Excipients suitable for use in granule compositions of the present invention may be suitable for use in wettable powder compositions of the present invention and vice versa.

[0082] The formulations can be prepared by any suitable method or technique, which will be appreciated by those of ordinary skill in the art. Such methods and techniques include, without limitation mixing, blending, extruding, drying, heating, combining, agitating, sieving and recovering, pulverizing, grinding, gelling, molding, and/or the like.

ACC

[0083] 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.

[0084] Specifically, ACC has been demonstrated to thin pome fruits and stone fruits. See U.S. Pat. No. 8,435,929. Reduction of the crop load on a tree (thinning) is often used to produce high quality tree fruit. During flowering and fruit set, growers commonly physically or chemically remove flowers (flower thinning) or young fruit (fruitlet thinning) to maximize the size and quality of the remaining fruit (Dennis, 2000, Plant Growth Reg. 31 : 1-16). U.S. Pat. No. 8,435,929 demonstrates that ACC provided more consistent thinning than ethephon.

[0085] ACC has been formulated in ready -to-use sprays and concentrated liquids. See, U.S. Pat. Application Publication No. 2018/0279621 and U.S. Pat. No. 10,517,299. In some embodiments, the ACC can be formulated as a ready to use spray or a concentrated liquid, such as like those of U.S. Pat. Application Publication No. 2018-0279621 and U.S. Pat. No. 10,517,299. Water-soluble granular formulations of ACC have also been described. See e.g., U.S. Pat. Application No. 2022/0240512. In some embodiments, the ACC is formulated as a water-soluble granular formulation as described in U.S. Pat. Application No. 2022/0240512. In some embodiments, the ACC is provided as a formulation of ACC. In some embodiments, the formulation of ACC is Accede® Plant Growth Regulator.

[0086] In some embodiments, the ACC is an ACC salt. 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, di gluconate, glycerophosphate, hemi sulfate, 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 quatemized 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. In some embodiments, the ACC salt is an ACC HC1 salt. In some embodiments, the ACC HC1 salt is one described in U.S. Pat. Application Pub. No. 20180279621. In some embodiments, the ACC or ACC salt is provided as a formulation. In some embodiments, the ACC formulation is any of those described in U.S. Pat. Application Pub. No. 20180279621 and US20200323214.

[0087] In some embodiments, the ACC is provided as a stabilized ACC formulation, such as any of those described in U.S. Pat. Application Pub. No. 20180279622.

[0088] In some embodiments, the ACC is an ACC hydrate or polymorph thereof. Hydrates of ACC suitable for use in the present disclosure include ACC trihydrate and ACC anhydrate.

Ethylene Inhibitors

[0089] In general, ethylene inhibitors are compounds that are effective to inhibit or reduce the activity of ethylene. In some embodiments, the ethylene inhibitor binds ethylene. In some embodiments, the ethylene inhibitor blocks ethylene binding an ethylene receptor. In some embodiments, the ethylene inhibitor reduces the amount of ethylene present in the plant or component thereof, such as a fruit or vegetable. In some embodiments, the ethylene inhibitor is an ACC synthase inhibitor. In some embodiments, the ethylene inhibitor is an ACC oxidase inhibitor. In some embodiments, the ethylene inhibitor reduces or prevents ethylene perception in the plant or component thereof (such as the fruit or vegetable). In some embodiments, the ethylene inhibitor inhibits ethylene biosynthesis in the plant or component thereof, such as a fruit or vegetable. Example ethylene inhibitors that can be used in the formulation of the present disclosure include, but are not limited to, aminoethoxy vinylgly cine (AVG) (including, but not limited to, 2-aminoethoxyvinyl glycine, N-acetyl aminoethoxyvinylglycine, a compound described in Mexico Patent Application Publication MXPA99002753A, U.S. Pat. No. 5,801,119, AVG hydrochloride (AVG HC1)), methoxyvinylglycine (MVG), silver or silver ions, silver thiosulphate, cobalt or cobalt ions, a cyclopropane (e.g., 1 -methylcyclopropene or any other set forth in U.S. Patent No. 5,518,988), a pyrazinamide or a derivative thereof (such as any one described in Sun et al., Nat. Commun., 2017, 8: 15758), 2,5-norbornadiene (2,5- NBD), diazocyclopentadiene (DACP), aminooxyacetic acid, or a compound or composition as set forth in Japanese Patent Publication JP4963568B2. In some embodiments, the ethylene inhibitor is AVG. In some embodiments, the ethylene inhibitor is a formulation of AVG. In some embodiments the formulation of AVG is ReTain® Plant Growth Regulator.

Exemplary Formulations

[0090] Described in certain example embodiments herein are fruit maturation formulations including an amount of an ethylene inhibitor; and an amount of 1 -amino- 1- cyclopropanecarboxylic acid (ACC), a salt thereof, hydrate thereof, or a polymorph thereof. In some embodiments, the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to reduce a negative effect of the ethylene inhibitor on a characteristic of a fruit as compared to a suitable control. In some embodiments, the characteristic is fruit color. In some embodiments, the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to enhance fruit color as compared to a fruit exposed to an ethylene inhibitor alone. In some embodiments, the amount of the ethylene inhibitor is effective to reduce pre-harvest fruit drop in a plant or tree. In some embodiments, the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof does not significantly impact the reduction in preharvest fruit drop in the plant or tree.

[0091] In some embodiments, the amount of the ethylene inhibitor ranges from about 100 g to about 1500 g, such as about 126 g to about 1261g; wherein the amount of the ethylene inhibitor ranges from about 100 mL to about 1500 mL, such as about 126 mL to about 1261 mL; wherein the amount of the ethylene inhibitor ranges from about 50 ppm to about 500 ppm; or wherein the amount of the ethylene inhibitor is present at about 15 percent wt/wt or v/v of the formulation. In some embodiments, the amount of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof ranges from about 350 g to about 4,000 g, such as about 378 g, to about 3784 g; wherein the amount of the ACC ranges from about 350 mL to about 4,000 mL, such as about 378 mL to about 3785 mL; wherein the amount of the ACC ranges from about 100 ppm to 1000 ppm; or wherein the amount of ACC is present at about 10 percent wt/wt or v/v of the formulation. In some embodiments, these amounts are based on per 100 gallons of water per acre.

[0092] In some embodiments, the ratio of the amount of the ethylene inhibitor to the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof is about 0.2-1.0 to 1.0.

[0093] In some embodiments, the ethylene inhibitor is aminoethoxyvinylglycine (AVG) (including, but not limited to, 2-aminoethoxyvinyl glycine, N-acetyl aminoethoxyvinylglycine, a compound described in Mexico Patent Application Publication MXPA99002753A, U.S. Pat. No. 5,801,119, and AVG hydrochloride (AVG HC1)), methoxyvinylglycine (MVG), silver or silver ions, silver thiosulphate, cobalt or cobalt ions, a cyclopropane (e.g., 1- methylcyclopropene (MCP) or any other set forth in U.S. Patent No. 5,518,988), a pyrazinamide or a derivative thereof (such as any one described in Sun et al., Nat. Commun., 2017, 8: 15758), 2,5-norbomadiene (2,5-NBD), diazocyclopentadiene (DACP), aminooxyacetic acid, or a compound or composition as set forth in Japanese Patent Publication JP4963568B2, or any combination thereof. In some embodiments, the ethylene inhibitor is AVG or MCP.

[0094] In some embodiments, the formulation is a concentrate that is diluted prior to use. In some embodiments, the concentrate formulation is diluted by 1-100 fold or more. In some embodiments, the formulation is a ready to use formulation. In some embodiments, the formulation is a solid or a liquid.

[0095] In some embodiments, the fruit is a pome fruit. In some embodiments, the fruit is an apple, peach, pear, or nectarine. In some embodiments, the apple is selected from the group of Idared, Braeburn, Cameo, Cortland, crabapple, Empire, Fuji, Gala, Ginger Gold, Golden Delicious, Granny Smith, Honeycrisp, Jonagold, Jonathan, McIntosh, Mutsu, Nittany, Pink Lady, Rome, Red Delicious, Stayman, Winesap and York. METHODS

[0096] The invention is also directed to a method of improving fruit maturation by reducing one or more negative effects of an ethylene inhibitor, such as fruit decoloring, that includes administering an amount of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof and an amount of an ethylene inhibitor to a plant or component thereof. In some embodiments, the method includes administering a formulation of the present disclosure to a plant or component thereof. In some embodiments, the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof is administered or applied simultaneously with the ethylene inhibitor (such as in a single formulation or two separate formulations applied at the same time). In some embodiments, the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof or formulation thereof is administered or applied separate from (such as in separate formulations applied a different times) the ethylene inhibitor or formulation thereof. In some embodiments, the ACC is administered before or after administration of the ethylene inhibitor. In some embodiments, administering includes the step of treating soil, a plant or a component thereof, such as the fruit, with an amount of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof and an amount of an ethylene inhibitor to the plant or a component thereof. The composition can be diluted with water or other liquid and spray-applied. In some embodiments, the plant is a fruitproducing plant, such as an apple tree, pear tree, peach tree, nectarine tree, etc. In some embodiments, the plant is a pome fruit tree. In some embodiments, the apple tree that the formulations of the present disclosure are applied or administered to are selected from the group of Idared, Braebum, Cameo, Cortland, crabapple, Empire, Fuji, Gala, Ginger Gold, Golden Delicious, Granny Smith, Honeycrisp, Jonagold, Jonathan, McIntosh, Mutsu, Nittany, Pink Lady, Rome, Red Delicious, Stayman, Winesap and York.

[0097] Any suitable method can be used to apply the formulation(s). They can be coated, sprayed, deposited, or otherwise applied by any conventional method that will be appreciated by those of ordinary skill in the art. In some embodiments, the formulation is a concentrate and is diluted in water or another liquid and sprayed on the plant or tree to be treated. The spraying may be by conventional ground or aerial application equipment. Spray volumes are variable depending upon the orchard or crop, growth stage and climatic conditions. The range may be 5 gallons to 300 gallons/acre or higher. A presently preferred range is between 250 to 300 gallons per acre by pressurized spray application equipment. To prepare a formulation for application, a tank is half-filled with water, followed by spray addition of adjuvant, and then addition of plant growth regulator, followed by addition of more water and then mixed for at least 15 minutes prior to actual spraying. [0098] In some embodiments, the formulation containing an ethylene inhibitor, ACC, or both, may be directly applied to the soil (in which the plant will be grown or is growing) with or without granular fertilizers for the improved growth and maintenance of crops.

[0099] The concentration of the active ingredient(s) will vary depending upon the type of fruit is to be treated, the peculiarities of the locale, and the desired result. In some embodiments, the ACC, the ethylene inhibitor, or a formulation of the present disclosure can be applied at a field rate of from about 0.02 to about 50/lbs per acre; preferably at a rate of from about 0.1 to about 5/lbs per acre and most preferably at a rate of from about 0.5 to about 3 Ibs/acre.

[0100] In some embodiments, one or more administrations or applications (e.g., 1, 2, 3, 4, 5, 6,7 8, 9, 10 or more administrations or applications) of the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof and/or ethylene inhibitor can be made to a plant, field, orchard, vineyard, etc. weekly, monthly, or yearly. In some embodiments, administration or application is once weekly, biweekly, every-other day, or daily. In some embodiments, administration or application is once weekly, biweekly, every-other day, or daily for 1 week, each of the 2 weeks, each of the 3 weeks, each of the 4 weeks, each of the 5 weeks, or each of the 6 weeks before the anticipated harvest date. In some embodiments, one administration or application each week is carried out for each of the 1-4 weeks prior to the anticipated harvest date. In some embodiments, one administration or application each week with 7 days apart from each administration or application is carried out for each of the 1-4 weeks prior to the anticipated harvest date. In some embodiments, application is in intervals. In some embodiments, the intervals are 7, 10, 14, or 21 days between applications.

[0101] The ACC, a salt thereof, a hydrate thereof, or a polymorph thereof and/or ethylene inhibitor, or formulation of the present disclosure can be applied one or more times to the plant or tree 1 - 4 weeks before the normal harvest. In some embodiments, the time interval between each application is 1-7 days. In some embodiments, the time interval between each application 7 days. In some embodiments, an ethylene inhibitor is applied alone first followed by 1 or more applications of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof or a formulation thereof. In some embodiments, about 4 weeks prior to harvest an ethylene inhibitor is applied alone, which is followed by weekly administrations of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof or a formulation thereof until harvest.

[0102] The ACC, a salt thereof, a hydrate thereof, or a polymorph thereof or a formulation thereof, and/or ethylene inhibitor, or formulation of the present disclosure may be applied to plants, soil in conjunction with other adjuvants. An adjuvant is a material added to a tank-mix to aid or modify the action of an agrichemical, or the physical characteristics of the mixture. There are several types of tank-mix adjuvants such as buffering agents, compatibility agents, defoaming agents, modified vegetable oil concentrates, non-ionic surfactants, penetrants, phytoblend oil, spreader/sticker, sticker, vegetable oil concentrates, or other components such as acidifiers, humectants, activators and crop oil concentrates. An example of a buffering agent is BUFFER-X, a mixture of alkylarylpolyethoxyethanol, fatty acids, glycol ethers, D-alkyl benzene dicarboxylate and isopropanol; an example of a compatibility agent is LATRON AG- 44M, a mixture of alkylarylpolyoxyethylene glycol and phosphate ester surfactants; an example of a defoamer is FOAM BUSTER, a dimethylpolysiloxane; examples of spreaderstickers are LATRON B-1956, a modified phthalic glycerol alkylated resin and SURFIX, a beta-pinene polymer and an example of a sticker is BOND, a synthetic latex polymer.

[0103] The type of adjuvant and application rate will vary depending upon the adjuvant used, crop, crop growth, climatic conditions, desired effect and which other tank mix additives, if any are utilized. Other tank mix additives may be pesticides or foliar nutrients for example. [0104] Delivery of the formulations or components thereof can be by any suitable method, formulation, or technique, including any of those set forth in U.S. Pat. No. 5,518,988; 6,017,849; 6,313,068; 6,444,619; 6,897,185; 6,762,153; 6,426,319; 6,770,600; International Patent Publication WO 9722249; WO 2002024171 and WO 2008089140.

Exemplary Methods

[0105] Described herein are methods of improving fruit maturation, such as by reducing one or more negative effects of an ethylene inhibitor, in a plant or tree, the method including applying to a plant an amount of an ethylene inhibitor; and applying to a plant an amount of 1- amino-1 -cyclopropanecarboxylic acid (ACC), a salt thereof, hydrate thereof, or a polymorph thereof. In some embodiments, the negative effect is or includes preventing fruit ripening, loss of flavor, undesirable texture, reduced nutritional value, undesirable color/discoloration, undesirable softening, decay development, undesirable flavors/off-flavors, or any combination thereof. Additional examples of negative effects of an ethylene inhibitor which the method described herein can improve include any of those negative effects of an ethylene inhibitor described in e.g., Martinez-Romero et al., Crit. Rev. Food. Sci., 2007, 47(6), 543-560.

[0106] In certain example embodiments, the amount of the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof are applied simultaneously. In certain example embodiments, the amount of the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof are contained in the same formulation. In certain example embodiments, the formulation is a formulation of the present disclosure. In some embodiments, the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof are contained in separate formulations. In some embodiments, the amount of the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, are applied at separate times.

[0107] In some embodiments, the amount of the ethylene inhibitor ranges from about 100 g to about 1500 g, such as about 126 g to about 1261g; wherein the amount of the ethylene inhibitor ranges from about 100 mL to about 1500 mL, such as about 126 mL to about 1261 mL; wherein the amount of the ethylene inhibitor ranges from about 50 ppm to about 500 ppm; or wherein the amount of the ethylene inhibitor is present at about 15 percent wt/wt or v/v of the formulation. In some embodiments, these amounts are based on per 100 gallons of water per acre. In some embodiments, the amount of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof ranges from about 350 g to about 4,000 g, such as about 378 g, to about 3784 g; wherein the amount of the ACC ranges from about 350 mL to about 4,000 mL, such as about 378 mL to about 3785 mL; wherein the amount of the ACC ranges from about 100 ppm to 1000 ppm; or wherein the amount of ACC is present at about 10 percent wt/wt or v/v of the formulation. In some embodiments, these amounts are based on per 100 gallons of water per acre. In some embodiments, the ratio of the amount of the ethylene inhibitor to the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof is about 0.2-1.0 to 1.0. In some embodiments, the ratio of the amount of the ethylene inhibitor to the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof is about 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 1 to 1 In some embodiments, the ratio of the amount of the ethylene inhibitor to the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof is about 0.4: 1. In some embodiments, these amounts are based on per 100 gallons of water per acre.

[0108] In some embodiments, the ethylene inhibitor is aminoethoxyvinylglycine (AVG) (including, but not limited to, 2-aminoethoxyvinyl glycine, N-acetyl aminoethoxyvinylglycine, a compound described in Mexico Patent Application Publication MXPA99002753A, U.S. Pat. No. 5,801,119, and AVG hydrochloride (AVG HC1)), methoxyvinylglycine (MVG), silver or silver ions, silver thiosulphate, cobalt or cobalt ions, a cyclopropane (e.g., 1- methylcyclopropene (MCP) or any other set forth in U.S. Patent No. 5,518,988), a pyrazinamide or a derivative thereof (such as any one described in Sun et al., Nat. Commun., 2017, 8: 15758), 2,5-norbomadiene (2,5-NBD), diazocyclopentadiene (DACP), aminooxyacetic acid, or a compound or composition as set forth in Japanese Patent Publication JP4963568B2, or any combination thereof. [0109] In some embodiments, the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to reduce a negative effect of the ethylene inhibitor on a characteristic of a fruit as compared to a suitable control. In some embodiments, the characteristic is fruit color. In some embodiments, the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to enhance fruit color as compared to a fruit exposed to an ethylene inhibitor alone. In some embodiments, the amount of the ethylene inhibitor is effective to reduce pre-harvest fruit drop in a plant or tree. In some embodiments, the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof does not significantly impact the reduction in pre-harvest fruit drop in the plant or tree.

[0110] In some embodiments, the fruit or plant or tree is a pome fruit, plant, or tree. In some embodiments, the fruit or plant, or tree is an apple, peach, pear, or nectarine fruit, plant, or tree.

EXAMPLES

[OHl] Now having described the embodiments of the present disclosure, in general, the following Examples describe some additional embodiments of the present disclosure. While embodiments of the present disclosure are described in connection with the following examples and the corresponding text and figures, there is no intent to limit embodiments of the present disclosure to this description. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of embodiments of the present disclosure. The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to perform the methods and use the probes disclosed and claimed herein. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C, and pressure is at or near atmospheric. Standard temperature and pressure are defined as 20 °C and 1 atmosphere.

Example 1

[0112] This Example evaluates a method of applying a mixture of AVG (an exemplary ethylene inhibitor) and 1 -aminocyclopropane- 1 -carboxylic acid (ACC) to apple trees and its effect on pre-harvest drop and fruit coloration. These data demonstrate at least that applying AVG alone before the anticipated harvest efficiently reduces pre-harvest drop but negatively affects red color formation. Conversely, ACC application increases red color but also leads to increased fruit drop in early-maturing cultivars when used close to the harvest window. This Example demonstrates the timing and concentrations for applying a combination of AVG and ACC for optimizing fruit retention and coloration. This can be especially advantageous when the harvest period for early-maturing cultivars is extended beyond the traditional window. In mid-season and late-maturing apple cultivars, single and multiple pre-harvest ACC applications increase red color intensity with negligible effect on pre-harvest drop. Similar effects are observed when ACC is mixed with other ethylene inhibitors, such as 1- Methylcyclopropene, as with the ACC-AVG mixture.

Methods

[0113] A field trial was conducted at the Alson H. Smith Jr. Agricultural Research and Extension Center in Winchester, VA, in 2023 and 2024 to evaluate the effectiveness of Accede when used alone and in combination with ReTain to enhance fruit color and reduce pre-harvest fruit drop in 'Honeycrisp' and 'Gala' apple varieties. In 'Honeycrisp', ReTain was applied once (three weeks before the harvest date), whereas Accede was applied three times (at 3, 2, and 1 week before the harvest date) as shown in Table 1. Trees were randomly assigned to each treatment, with six replicates for 'Honeycrisp' — three for assessing fruit drop and quality, and three for molecular and biochemical analyses. For 'Gala', only Accede was tested against control in 2023 and 2024, with three replicates used (Table 1). The volume of spray for each treatment was adjusted to 100 gallons per acre, and Regulaid at a rate of 2 pints per 100 gallons was included in all treatments. Accede® Plant Growth Regulator and ReTain® Plant Growth Regulator were mixed to produce a formulation containing 10% Accede® Plant Growth Regulator and 15% ReTain® Plant Growth Regulator. Fruit drop percentage was calculated as the number of fruits remaining on each tree is assessed against an initial count of 100 fruits. Color was evaluated by determining IAD (Index of Absorbance Difference) as measured by the DA meter, which is a tool for estimating chlorophyll content in fruit skin nondestructively. It measures absorbance at two wavelengths: 670 nm, which is the peak absorbance for chlorophyll in stone fruit, and 720 nm, a wavelength with minimal absorbance unaffected by chlorophyll degradation in the peel. Notably, higher IAD values indicate higher chlorophyll content and correspond to less red color formation in the fruit. In addition to chlorophyll degradation, for red color assessment in 2024, color intensity was measured as hue angle (h°) using a colorimeter. Hue angle is the most appropriate way of representing changes in color, refers to the line from the origin to the intercept of a* (x-axis) and b* (y-axis) coordinates, where 0° = red, 90° = yellow, 180° = green, and 270° = blue. Results

[0114] The results are shown in Tables 1, 2, 3, 4 and 5 and FIG. 1, FIG. 2 and FIG. 3. Table 1 shows the List of PGRs, active ingredients and doses for 100 gal/acre for ‘Honey crisp’ and ‘Gala’ apple cultivars.

[0115] Table 2 shows the effect of combining Accede® Plant Growth Regulator and ReTain® Plant Growth Regulator on improving fruit color and minimizing fruit drop in 'Honey crisp' apples in 2023.

[0116] Table 3 shows the effect of combining Accede® Plant Growth Regulator and Re Tain® Plant Growth Regulator on improving fruit color and minimizing fruit drop in 'Honeycrisp' apples in 2024.

[0117] Table 4 shows DA meter reading (IAD) for changes in chlorophyll content in Accede-treated and untreated (control) in ‘Gala’ apples 2023.

[0118] Table 5 shows DA meter reading (IAD) for changes in chlorophyll breakdown and hue angle for color intensity in Accede-treated and untreated (control) at normal harvest date in 'Gala' apples 2024.

[0119] FIG. 1 shows the influence of Accede® Plant Growth Regulator and ReTain® Plant Growth Regulator mixture on enhancing fruit in 'Honeycrisp' Apples at standard harvest time and two-weeks post-harvest in 2023. [0120] FIG. 2 shows the influence of Accede® Plant Growth Regulator on enhancing fruit coloration in 'Gala' Apples at standard harvest time and two-weeks post-harvest in 2023.

[0121] FIG. 3 shows the influence of Accede® Plant Growth Regulator and ReTain® Plant Growth Regulator mixture on enhancing fruit in 'Honeycrisp' Apples at standard harvest time and two-weeks post-harvest in 2024.

[0122] FIG. 4 shows the influence of Accede® Plant Growth Regulator on enhancing fruit coloration in 'Gala' Apples at standard harvest time in 2024.

***

[0123] Various modifications and variations of the described methods, pharmaceutical compositions, and kits of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific embodiments, it will be understood that it is capable of further modifications and that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention that are obvious to those skilled in the art are intended to be within the scope of the invention. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure come within known customary practice within the art to which the invention pertains and may be applied to the essential features herein before set forth.

[0124] Further attributes, features, and embodiments of the present invention can be understood by reference to the following numbered aspects of the disclosed invention. Reference to disclosure in any of the preceding aspects is applicable to any preceding numbered aspect and to any combination of any number of preceding aspects, as recognized by appropriate antecedent disclosure in any combination of preceding aspects that can be made. The following numbered aspects are provided:

1. A fruit maturation formulation comprising: an amount of an ethylene inhibitor; and an amount of 1 -amino- 1 -cyclopropanecarboxylic acid (ACC), a salt thereof, hydrate thereof, or a polymorph thereof.

2. The formulation of aspect 1, wherein the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to reduce a negative effect of the ethylene inhibitor on a characteristic of a fruit as compared to a suitable control. 3. The formulation of aspect 2, wherein the characteristic is fruit color.

4. The formulation of any one of aspects 1-3, wherein the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to enhance fruit color as compared to a fruit exposed to an ethylene inhibitor alone or an untreated control.

5. The formulation of any one of aspects 1-4, wherein the amount of the ethylene inhibitor is effective to reduce pre-harvest fruit drop in a plant or tree.

6. The formulation of aspect 6, wherein the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof does not significantly impact the reduction in pre-harvest fruit drop in the plant or tree.

7. The formulation of any one of aspects 1-6, wherein the amount of the ethylene inhibitor ranges from about 100 g to about 1500 g, such as about 126 g to about 1261g; wherein the amount of the ethylene inhibitor ranges from about 100 mL to about 1500 mL, such as about 126 mL to about 1261 mL; wherein the amount of the ethylene inhibitor ranges from about 50 ppm to about 500 ppm; or wherein the amount of the ethylene inhibitor is present at about 15 percent wt/wt or v/v of the formulation.

8. The formulation of any one of aspects 1-7, wherein the amount of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof ranges from about 350 g to about 4,000 g, such as about 378 g, to about 3784 g; wherein the amount of the ACC ranges from about 350 mL to about 4,000 mL, such as about 378 mL to about 3785 mL; wherein the amount of the ACC ranges from about 100 ppm to 1000 ppm; or wherein the amount of ACC is present at about 10 percent wt/wt or v/v of the formulation.

9. The formulation of any one of aspects 1-8, wherein the ratio of the amount of the ethylene inhibitor to the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof is about 1.0 to 1.0.

10. The formulation of any one of aspects 1-9, wherein the ethylene inhibitor is aminoethoxy vinylgly cine (AVG) (including, but not limited to, 2-aminoethoxy vinyl glycine, N-acetyl aminoethoxyvinylglycine, a compound described in Mexico Patent Application Publication MXPA99002753A, U.S. Pat. No. 5,801,119, and AVG hydrochloride (AVG HC1)), methoxyvinylglycine (MVG), silver or silver ions, silver thiosulphate, cobalt or cobalt ions, a cyclopropane (e.g., 1 -methylcyclopropene (MCP) or any other set forth in U.S. Patent No. 5,518,988), a pyrazinamide or a derivative thereof (such as any one described in Sun et al., Nat. Commun., 2017, 8: 15758), 2,5-norbomadiene (2,5-NBD), diazocyclopentadiene (DACP), aminooxyacetic acid, or a compound or composition as set forth in Japanese Patent Publication JP4963568B2, or any combination thereof.

11. The formulation of aspect 10, wherein the ethylene inhibitor is AVG or MCP.

12. The formulation of any one of aspects 1-11, wherein the formulation is a concentrate.

13. The formulation of any one of aspects 1-12, wherein the formulation is ready to use.

14. The formulation of any one of aspects 1-13, wherein the formulation is a solid or a liquid.

15. The formulation of any one of aspects 2-14, wherein the fruit is a pome fruit.

16. The formulation of any one of aspects 2-14, wherein the fruit is an apple, peach, pear, or nectarine.

17. A method of improving fruit maturation in a plant or tree, the method comprising: applying to a plant an amount of an ethylene inhibitor; and applying to a plant an amount of 1 -amino- 1 -cyclopropanecarboxylic acid (ACC), a salt thereof, hydrate thereof, or a polymorph thereof.

18. The method of aspect 17, wherein the amount of the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof are applied simultaneously. 19. The method of any one of aspects 17-18, wherein the amount of the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof are contained in the same formulation.

20. The method of aspect 19, wherein the formulation is a formulation of any one of aspects 1-16.

21. The method of any one of aspects 17-18, wherein the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof are contained in separate formulations.

22. The method of aspect 17, wherein the amount of the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, are applied at separate times.

23. The method of any one of aspects 17-22, wherein the amount of the ethylene inhibitor ranges from about 100 g to about 1500 g, such as about 126 g to about 1261g; wherein the amount of the ethylene inhibitor ranges from about 100 mL to about 1500 mL, such as about 126 mL to about 1261 mL; wherein the amount of the ethylene inhibitor ranges from about 50 ppm to about 500 ppm; or wherein the amount of the ethylene inhibitor is present at about 15 percent wt/wt or v/v of the formulation.

24. The method of any one of aspects 17-23, wherein the amount of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof ranges from about 350 g to about 4,000 g, such as about 378 g, to about 3784 g; wherein the amount of the ACC ranges from about 350 mL to about 4,000 mL, such as about 378 mL to about 3785 mL; wherein the amount of the ACC ranges from about 100 ppm to 1000 ppm; or wherein the amount of ACC is present at about 10 percent wt/wt or v/v of the formulation.

25. The method of any one of aspects 17-24, wherein the ratio of the amount of the ethylene inhibitor to the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof is about 0.2-1. O to 1.0. 26. The method of any one of aspects 17-25, wherein the ethylene inhibitor is aminoethoxy vinylgly cine (AVG) (including, but not limited to, 2-aminoethoxy vinyl glycine, N-acetyl aminoethoxyvinylglycine, a compound described in Mexico Patent Application Publication MXPA99002753A, U.S. Pat. No. 5,801,119, and AVG hydrochloride (AVG HC1)), methoxyvinylglycine (MVG), silver or silver ions, silver thiosulphate, cobalt or cobalt ions, a cyclopropane (e.g., 1 -methylcyclopropene (MCP) or any other set forth in U.S. Patent No. 5,518,988), a pyrazinamide or a derivative thereof (such as any one described in Sun et al., Nat. Commun., 2017, 8: 15758), 2,5-norbomadiene (2,5-NBD), diazocyclopentadiene (DACP), aminooxyacetic acid, or a compound or composition as set forth in Japanese Patent Publication JP4963568B2, or any combination thereof.

27. The method of any one of aspects 17-26, wherein the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to reduce a negative effect of the ethylene inhibitor on a characteristic of a fruit as compared to a suitable control.

28. The method of aspect 26, wherein the characteristic is fruit color.

29. The method of any one of aspects 17-28, wherein the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to enhance fruit color as compared to a fruit exposed to an ethylene inhibitor alone.

30. The method of any one of aspects 17-29, wherein the amount of the ethylene inhibitor is effective to reduce pre-harvest fruit drop in a plant or tree.

31. The method of aspect 30, wherein the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof does not significantly impact the reduction in pre-harvest fruit drop in the plant or tree.

32. The method of any one of aspects 17-31, wherein the fruit or plant or tree is a pome fruit, plant, or tree.

33. The method of any one of aspects 17-31, wherein the fruit or plant, or tree is an apple, peach, pear, or nectarine fruit, plant, or tree.

Claims

CLAIMS What is claimed is:

2. The formulation of claim 1, wherein the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to reduce a negative effect of the ethylene inhibitor on a characteristic of a fruit as compared to a suitable control.

3. The formulation of claim 2, wherein the characteristic is fruit color.

4. The formulation of claim 1, wherein the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to enhance fruit color as compared to a fruit exposed to an ethylene inhibitor alone or an untreated control.

5. The formulation of claim 1 , wherein the amount of the ethylene inhibitor is effective to reduce pre-harvest fruit drop in a plant or tree.

6. The formulation of claim 6, wherein the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof does not significantly impact the reduction in pre-harvest fruit drop in the plant or tree.

7. The formulation of claim 1, wherein the amount of the ethylene inhibitor ranges from about 100 g to about 1500 g, such as about 126 g to about 1261g; wherein the amount of the ethylene inhibitor ranges from about 100 mL to about 1500 mL, such as about 126 mL to about 1261 mL; wherein the amount of the ethylene inhibitor ranges from about 50 ppm to about 500 ppm; or wherein the amount of the ethylene inhibitor is present at about 15 percent wt/wt or v/v of the formulation.

8. The formulation of claim 1, wherein the amount of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof ranges from about 350 g to about 4,000 g, such as about 378 g, to about 3784 g; wherein the amount of the ACC ranges from about 350 mL to about 4,000 mL, such as about 378 mL to about 3785 mL; wherein the amount of the ACC ranges from about 100 ppm to 1000 ppm; or wherein the amount of ACC is present at about 10 percent wt/wt or v/v of the formulation.

9. The formulation of any one of the preceding claims, wherein the ratio of the amount of the ethylene inhibitor to the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof is about 1.0 to 1.0.

10. The formulation of claim 1, wherein the ethylene inhibitor comprises or consists of aminoethoxyvinylglycine (AVG), AVG hydrochloride (AVG HC1)), methoxyvinylglycine (MVG), silver or silver ions, silver thiosulphate, cobalt or cobalt ions, a cyclopropane (e.g., 1- methylcyclopropene (MCP), a pyrazinamide or a derivative thereof, 2,5-norbornadiene (2,5- NBD), diazocyclopentadiene (DACP), aminooxyacetic acid, or any combination thereof.

11. The formulation of claim 10, wherein the ethylene inhibitor is AVG or MCP.

12. The formulation of claim 1, wherein the formulation is a concentrate.

13. The formulation of claim 1, wherein the formulation is ready to use.

14. The formulation of claim 1, wherein the formulation is a solid or a liquid.

15. The formulation of claim 2, wherein the fruit is a pome fruit.

16. The formulation of claim 2, wherein the fruit is an apple, peach, pear, or nectarine.

18. The method of claim 17, wherein the amount of the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof are applied simultaneously.

19. The method of claim 17, wherein the amount of the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof are contained in the same formulation.

20. The method of claim 19, wherein the formulation is a formulation of claim 1.

21. The method of claim 17, wherein the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof are contained in separate formulations.

22. The method of claim 17, wherein the amount of the ethylene inhibitor and the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, are applied at separate times.

23. The method of claim 17, wherein the amount of the ethylene inhibitor ranges from about 100 g to about 1500 g, such as about 126 g to about 1261g; wherein the amount of the ethylene inhibitor ranges from about 100 mL to about 1500 mL, such as about 126 mL to about 1261 mL; wherein the amount of the ethylene inhibitor ranges from about 50 ppm to about 500 ppm; or wherein the amount of the ethylene inhibitor is present at about 15 percent wt/wt or v/v of the formulation.

24. The method of claim 17, wherein the amount of ACC, a salt thereof, a hydrate thereof, or a polymorph thereof ranges from about 350 g to about 4,000 g, such as about 378 g, to about 3784 g; wherein the amount of the ACC ranges from about 350 mL to about 4,000 mL, such as about 378 mL to about 3785 mL; wherein the amount of the ACC ranges from about 100 ppm to 1000 ppm; or wherein the amount of ACC is present at about 10 percent wt/wt or v/v of the formulation.

25. The method of claim 17, wherein the ratio of the amount of the ethylene inhibitor to the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof is about 0.2-1.0 to 1.0.

26. The method of claim 17, wherein the ethylene inhibitor is aminoethoxyvinylglycine (AVG) (including, but not limited to, 2-aminoethoxyvinyl glycine, N-acetyl aminoethoxyvinylglycine, a compound described in Mexico Patent Application Publication MXPA99002753A, U.S. Pat. No. 5,801,119, and AVG hydrochloride (AVG HC1)), methoxyvinylglycine (MVG), silver or silver ions, silver thiosulphate, cobalt or cobalt ions, a cyclopropane (e.g., 1 -methylcyclopropene (MCP) or any other set forth in U.S. Patent No. 5,518,988), a pyrazinamide or a derivative thereof (such as any one described in Sun et al., Nat. Commun., 2017, 8: 15758), 2,5-norbomadiene (2,5-NBD), diazocyclopentadiene (DACP), aminooxyacetic acid, or a compound or composition as set forth in Japanese Patent Publication JP4963568B2, or any combination thereof.

27. The method of claim 17, wherein the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to reduce a negative effect of the ethylene inhibitor on a characteristic of a fruit as compared to a suitable control.

28. The method of claim 26, wherein the characteristic is fruit color.

29. The method of claim 17, wherein the amount of the ACC, a salt thereof, hydrate thereof, or a polymorph thereof, is effective to enhance fruit color as compared to a fruit exposed to an ethylene inhibitor alone.

30. The method of claim 17, wherein the amount of the ethylene inhibitor is effective to reduce pre-harvest fruit drop in a plant or tree.

31. The method of claim 30, wherein the ACC, a salt thereof, a hydrate thereof, or a polymorph thereof does not significantly impact the reduction in pre-harvest fruit drop in the plant or tree.

32. The method of claim 17, wherein the fruit or plant or tree is a pome fruit, plant, or tree.

33. The method of claim 17, wherein the fruit or plant, or tree is an apple, peach, pear, or nectarine fruit, plant, or tree.