Improved release of ascaroside

Abstract

The present application relates to improved release compounds and compositions comprising one or more ascarosides, which can be applied to plants to provide enhanced disease resistance. Certain compounds are structurally modified ascaroside, e.g., in the form of an ascaroside-containing polymer. Certain compounds are physically modified ascaroside in a form in which one or more ascaroside is mixed with an organic and / or inorganic component.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 336,738, filed on April 29, 2022, entitled “IMPROVED RELEASE OF ACAROSIDES,” which is incorporated herein by reference. Technical Field

[0003] The present application generally relates to agrochemical compounds, compositions and methods for treating plants to enhance resistance to pathogens. Background Art

[0004] Ascaroside natural products are secondary metabolites produced by nematodes. A large number of structurally diverse ascarosides have been found in nature, and these molecules are thought to function as an evolutionarily conserved chemical language that nematodes use to control multiple aspects of their development. Ascarosides are also sensed by other organisms and have been shown to have a range of effects on a variety of organisms including bacteria, fungi, plants, and mammals, including humans. Ascarosides have the potential to be used as human pharmaceuticals, agrochemicals, and products for other diverse and valuable applications.

[0005] Studies have shown that when ascarosides are applied to plants, ascaroside treatment can enhance plant resistance to certain pathogens by inducing or activating one or more plant defense responses, which can inhibit pathogen growth and / or infection. By activating and / or activating the plant's innate defenses, ascarosides can thereby prevent the proliferation of pathogens and / or protect crops from the destructive effects of pathogens.

[0006] The application of agricultural chemicals to plants and the surrounding soil often results in various adverse effects, such as runoff / drift. It would be useful to provide compositions and methods that can provide improved release of these compounds to plants during growth. Summary of the invention

[0007] The present disclosure provides compositions and methods for the modified release of ascarosides. In some embodiments, the modified release is achieved by structurally altering the ascaroside molecule. In other embodiments, the modified release is provided by a composition-based method, which may or may not produce structural changes to the ascarosides contained in the formulation. The present disclosure also provides methods for extending the time that ascaroside-based treatments can affect the modulation of plant disease resistance.

[0008] Ascarosides are biodegradable and have been shown to rapidly decompose in soil and be metabolized by other organisms, including plants. This presents challenges for some commercial uses of ascarosides. For example, in agricultural settings, it may be desirable to apply ascarosides as seed treatments or to provide ascarosides via in-furrow application at the time of crop planting; in pharmaceutical applications, it may be desirable to develop time-release or implantable devices that release ascarosides over time. In the case of plants, the inventors have observed that such applications are not always reliable and hypothesize that this is because the ascaroside molecules decompose before they are taken up by the crop plant. For example, if seeds coated with a seed treatment containing unmodified ascarosides take a week or more to germinate, there is a risk that a large portion of the ascarosides in the coating will biodegrade upon contact with soil before the plant germinates from the seed. This may result in the failure or attenuation of the expected ascaroside-based reactions in the germinating plant. To address this problem, the present invention provides ascaroside compositions that are not susceptible to rapid biodegradation and / or are designed to release ascarosides over an extended period of time. Such delayed or extended release increases the chances that the crop plant will absorb or respond to the ascarosides and improves the reliability and / or convenience of applying such products.

[0009] The present disclosure includes, but is not limited to, the following embodiments.

[0010] Embodiment 1: A structurally modified ascaroside selected from the group consisting of: a) an ascaroside-based oligomer or polymer comprising two or more ascaroside moieties, optionally comprising a linker moiety between adjacent ascaroside moieties; b) an oligomer or polymer functionalized ascaroside comprising an ascaroside moiety and one, two or three oligomers or polymers attached thereto; and c) an ascaroside-pendent polymer comprising a polymer and one or more pendant ascaroside moieties attached thereto, optionally comprising a linker moiety between the polymer and the pendant ascaroside moieties.

[0011] Embodiment 2: The structurally modified ascaroside of embodiment 1, wherein the modified ascaroside is an ascaroside-based oligomer or polymer, and wherein the oligomer or polymer comprises two or more ascaroside moieties and has no linker moiety between adjacent ascaroside moieties.

[0012] Embodiment 3: A structurally modified ascaroside as described in Embodiment 1 or Embodiment 2, wherein the modified ascaroside is an ascaroside-based oligomer or polymer, and wherein adjacent ascaroside moieties are attached to each other via an ester bond formed by a hydroxyl group on a first ascaroside molecule and a carboxylic acid on a second ascaroside molecule.

[0013] Embodiment 4: The structurally modified ascaroside of embodiment 1, wherein the modified ascaroside is an ascaroside-based oligomer or polymer, and wherein the oligomer or polymer comprises two or more ascaroside moieties and has a linker moiety between adjacent ascaroside moieties.

[0014] Embodiment 5: The structurally modified ascaroside of Embodiment 1, wherein the linker moiety is selected from the group consisting of ether, ester, amide, glycoside, urethane, carbonate, and siloxane moieties.

[0015] Embodiment 6: The structurally modified ascaroside of any one of Embodiments 1 to 5, wherein the modified ascaroside is an ascaroside-based oligomer or polymer, wherein the oligomer or polymer comprises from two to one thousand ascaroside moieties.

[0016] Embodiment 7: The structurally modified ascaroside of Embodiment 6, wherein the oligomer or polymer comprises from two to five hundred ascaroside moieties.

[0017] Embodiment 8: The structurally modified ascaroside of Embodiment 6, wherein the oligomer or polymer comprises from two to one hundred ascaroside moieties.

[0018] Embodiment 9: The structurally modified ascaroside of Embodiment 6, wherein the oligomer or polymer comprises two to ten ascaroside moieties.

[0019] Embodiment 10: The structurally modified ascaroside of Embodiment 6, wherein the oligomer or polymer comprises at least ten ascaroside moieties.

[0020] Embodiment 11: The structurally modified ascaroside of Embodiment 6, wherein the oligomer or polymer comprises at least twenty ascaroside moieties.

[0021] Embodiment 12: The structurally modified ascaroside of Embodiment 6, wherein the oligomer or polymer comprises at least fifty ascaroside moieties.

[0022] Embodiment 13: The structurally modified ascaroside of Embodiment 1, wherein the modified ascaroside is an oligomer or polymer functionalized ascaroside comprising an oligomer or polymer attached to the ascaroside.

[0023] Embodiment 14: The structurally modified ascaroside of Embodiment 1, wherein the modified ascaroside is an oligomer or polymer functionalized ascaroside comprising two oligomers or polymers attached to the ascaroside.

[0024] Embodiment 15: The structurally modified ascaroside of Embodiment 1, wherein the modified ascaroside is an oligomer or polymer functionalized ascaroside comprising three oligomers or polymers attached to the ascaroside.

[0025] Embodiment 16: The structurally modified ascaroside of Embodiment 1, wherein the modified ascaroside is an ascaroside-pendent polymer comprising from about five to about five hundred ascaroside moieties attached thereto.

[0026] Embodiment 17: The structurally modified ascaroside of Embodiment 1 or Embodiment 16, wherein the modified ascaroside is a polymer with pendant ascarosides, and wherein the one or more pendant ascaroside moieties are directly bonded to the polymer.

[0027] Embodiment 18: The structurally modified ascaroside of Embodiment 1 or Embodiment 16, wherein the modified ascaroside is a polymer flanked by ascarosides comprising a linker moiety between the polymer and the one or more flanking ascaroside moieties.

[0028] Embodiment 19: The structurally modified ascaroside of Embodiment 18, wherein the linker moiety is selected from the group consisting of ether, ester, amide, glycoside, urethane, carbonate, and siloxane moieties.

[0029] Embodiment 20: The structurally modified ascaroside of any one of Embodiments 13 to 19, wherein the oligomer or polymer comprises a biodegradable polymer.

[0030] Embodiment 21: A structurally modified ascaroside as described in any of Embodiments 13 to 20, wherein the oligomer or polymer is selected from the group consisting of: chitosan, chitin, starch, lignin, agar, pectin, cellulose, other polysaccharides (e.g., bark, sawdust, other cellulosic wastes), poly(ethylene glycol), poly(caprolactone), poly(lactide), poly(glycolic acid), polybutene, poly(vinyl alcohol), poly(vinyl chloride), poly(citric acid), poly(acrylates), poly(aspartic acid), poly(ethylene), polyethylene vinyl acetate (PEVA), polystyrene, divinylbenzene, and their derivatives and copolymers.

[0031] Embodiment 22: A structurally modified ascaroside as described in any one of Embodiments 1 to 21, wherein the ascaroside portion has structure (I)

[0032]

[0033] in:

[0034] Z is an optionally substituted C 3-40 aliphatic group, and R aand R b Each of the following is independently -H, or an optionally substituted moiety selected from the group consisting of: C 1-20 Aliphatic group, C 1-20 Acyl, C 1-20 Heteroaliphatic, aryl, heteroaryl, hydroxyl protecting group, phosphorus-linked functional group, sulfur-linked functional group, silicon-linked functional group, C 2-20 Carbonate (e.g. part -C(O)OR c ), C 2-20 Carbamate (e.g., part -C(O)N(R c )2) C 2-20 Thioesters (e.g., moieties -C(S)R c ), C 2-20 Thiocarbonates (e.g., moieties -C(S)OR c ), C 2-20 Dithiocarbonates (e.g., part-C(S)SR c ), C 1-20 Thiocarbamates (e.g., moieties -C(S)N(R c ) 2), a sugar moiety, a peptide, a polymer chain, or a linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety, wherein R c is independently selected at each occurrence from -H, optionally substituted C 1-12 aliphatic, optionally substituted C 1-12 heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, a polymer chain, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety, and wherein R a and R b Can be taken together to form an optionally substituted ring, optionally containing one or more heteroatoms, and optionally containing one or more sites of unsaturation.

[0035] Embodiment 23: The structurally modified ascaroside of Embodiment 22, wherein Z is selected from the group consisting of:

[0036] i.–CH(CH3)–R 1 , where R 1 is an optionally substituted C 1-40 Aliphatic group

[0037] ii.–CH(CH3)–(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0038] iii.–CH(CH3)–(CH2) n –CH=CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0039] iv.–CH(CH3)–(CH2) n –CH(OH)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0040] v.–CH(CH3)–(CH2) n –C(O)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0041] vi.–(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0042] vii.–(CH2) n –CH=CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0043] viii.–(CH2) n –CH(OH)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0044] ix.–(CH2) n –C(O)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0045] x.–CH(CH3)–(CH2) n –CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0046] xi.–CH(CH3)–(CH2) n –CH=CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0047] xii.–CH(CH3)–(CH2) n –CH(OH)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0048] xiii.–CH(CH3)–(CH2) n –C(O)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0049] xiv.–(CH2) n –CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0050] xv.–(CH2) n –CH=CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0051] xvi.–(CH2) n –CH(OH)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; or

[0052] xvii.–(CH2) n –C(O)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety.

[0053] Embodiment 24: The structurally modified ascaroside according to Embodiment 23, wherein R a and R b Each is -H.

[0054] Embodiment 25: A structurally modified ascaroside as described in any one of Embodiments 22 to 24, wherein Z is -CH(CH3)-(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide

[0055] Embodiment 26: The structurally modified ascaroside of any one of Embodiments 1 to 25, wherein at least one of the ascaroside moieties is ascr#18.

[0056] Embodiment 27: A physically modified ascaroside comprising one or more ascarosides compounded with an organic material or an inorganic material.

[0057] Embodiment 28: The physically modified ascaroside of Embodiment 27, wherein the ascaroside is compounded with an organic material selected from coconut shell fiber, peat and / or pine bark.

[0058] Embodiment 29: The physically modified ascaroside of Embodiment 27, wherein the ascaroside is compounded with a polymer resin.

[0059] Embodiment 30: The physically modified ascaroside of Embodiment 29, wherein the polymer resin is a biodegradable polymer.

[0060] Embodiment 31: The physically modified ascaroside of Embodiment 29 or Embodiment 30, wherein the polymer resin is a melt processable polymer.

[0061] Embodiment 32: A physically modified ascaroside as described in any of Embodiments 29 to 31, wherein the polymer resin is selected from the group consisting of polypropylene, polyethylene, poly(vinyl chloride), polystyrene, polyethylene terephthalate, polyethylene-vinyl acetate, polyurethane, acrylonitrile butadiene styrene (ABS), nylon, vegetable starch, polylactic acid (PLA), polyhydroxyalkanoate (PHA), and derivatives and copolymers of any two or more thereof.

[0062] Embodiment 33: The physically modified ascaroside of Embodiment 27, wherein the ascaroside is compounded with an inorganic material selected from the group consisting of perlite, vermiculite, sand, clay, talc, wood flour, peat, silica gel, mica, activated carbon, and combinations thereof.

[0063] Embodiment 34: The physically modified ascaroside of Embodiment 27, wherein the ascaroside is compounded with an inorganic material selected from the group consisting of fertilizers (e.g., ammonium phosphate, ammonium sulfate, urea, potassium chloride, superphosphate), herbicides (e.g., sodium chlorate or sodium sulfate), insoluble siliceous materials (e.g., sand or crushed walnut shells), clay materials (e.g., montmorillonite, kaolinite or other types of clay), diatomaceous earth, granulated corn cobs, saponite, quartz, lead, iron, and agricultural minerals (e.g., sulfur, gypsum, lime, calcium carbonate, etc.), and combinations thereof.

[0064] Embodiment 35: The physically modified ascaroside of any one of Embodiments 27 to 34, comprising one or more bonds between one or more of the ascarosides and the organic material or the inorganic material.

[0065] Embodiment 36: A physically modified ascaroside as described in any of Embodiments 27 to 36, further comprising one or more additional components selected from the group consisting of surfactants, including emulsifiers, dispersants, foam formers, colorants, processing aids, lubricants, fillers, reinforcing agents, flame retardants, light stabilizers, ultraviolet radiation absorbers, weathering stabilizers, plasticizers, release agents, fragrances, thermal insulation additives (e.g., silica), cross-linking agents, antioxidants, defoamers, buffers, pH adjusters, compatibilizers, drift control additives, extenders / stickers, tackifiers, plant penetrants, safeners, spreaders, and wetting agents.

[0066] Embodiment 37: The physically modified ascaroside of any one of Embodiments 27 to 36, wherein at least one of the ascaroside has structure (I)

[0067]

[0068] in:

[0069] Z is an optionally substituted C 3-40 an aliphatic group, and

[0070] R a and R b Each of which is independently -H, or an optionally substituted moiety selected from the group consisting of: C 1-20 Aliphatic group, C 1-20 Acyl, C 1-20Heteroaliphatic, aryl, heteroaryl, hydroxyl protecting group, phosphorus-linked functional group, sulfur-linked functional group, silicon-linked functional group, C 2-20 Carbonate (e.g. part -C(O)OR c ), C 2-20 Carbamate (e.g., part -C(O)N(R c )2) C 2-20 Thioesters (e.g., moieties -C(S)R c ), C 2-20 Thiocarbonates (e.g., moieties -C(S)OR c ), C 2-20 Dithiocarbonates (e.g., part-C(S)SR c ), C 1-20 Thiocarbamates (e.g., moieties -C(S)N(R c ) 2), a sugar moiety, a peptide, a polymer chain, or a linker to another ascaroside molecule via a bond or a carbon-containing linker. c is independently selected at each occurrence from -H, optionally substituted C 1-12 aliphatic, optionally substituted C 1-12 heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, a polymer chain, or a linker to another ascaroside molecule via a bond or a carbon-containing linker, and wherein R a and R b Together they may form an optionally substituted ring, optionally containing one or more heteroatoms, and optionally containing one or more sites of unsaturation.

[0071] Embodiment 38: The physically modified ascaroside of Embodiment 37, wherein Z is selected from the group consisting of:

[0072] i.–CH(CH3)–R 1 , where R 1 is an optionally substituted C 1-40 Aliphatic group

[0073] ii.–CH(CH3)–(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0074] iii.–CH(CH3)–(CH2) n –CH=CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0075] iv.–CH(CH3)–(CH2) n –CH(OH)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0076] v.–CH(CH3)–(CH2) n –C(O)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0077] vi.–(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0078] vii.–(CH2) n –CH=CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0079] viii.–(CH2) n –CH(OH)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0080] ix.–(CH2) n –C(O)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide;

[0081] x.–CH(CH3)–(CH2) n –CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0082] xi.–CH(CH3)–(CH2) n –CH=CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0083] xii.–CH(CH3)–(CH2) n –CH(OH)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0084] xiii.–CH(CH3)–(CH2) n –C(O)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0085] xiv.–(CH2)n –CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0086] xv.–(CH2) n –CH=CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0087] xvi.–(CH2) n –CH(OH)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; or

[0088] xvii.–(CH2) n –C(O)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety.

[0089] Embodiment 39: A physically modified ascaroside as described in Embodiment 37 or Embodiment 38, wherein R a and R b Each is -H.

[0090] Embodiment 40: A physically modified ascaroside as described in any one of Embodiments 37 to 39, wherein Z is -CH(CH3)-(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide

[0091] Embodiment 41: The physically modified ascaroside of any one of Embodiments 27 to 40, wherein at least one of the ascaroside moieties is ascr#18.

[0092] Embodiment 42: A composition comprising a structurally modified ascaroside as described in any one of Embodiments 1 to 26 and / or a physically modified ascaroside as described in any one of Embodiments 27 to 41 and one or more agronomically acceptable excipients or additives.

[0093] Embodiment 43: The composition of Embodiment 42, which is in liquid form.

[0094] Embodiment 44: The composition of Embodiment 43, wherein the liquid is a sprayable formulation.

[0095] Embodiment 45: The composition of Embodiment 42, which is in solid form.

[0096] Embodiment 46: The composition of Embodiment 45, wherein the solid comprises particles.

[0097] Embodiment 47: The composition of Embodiment 45, wherein the solid comprises a plastic covering.

[0098] Embodiment 48: The composition of Embodiment 45, wherein the solid composition is a film.

[0099] Embodiment 49: A method comprising contacting a plant or a part thereof, or soil surrounding the plant or a part thereof, with a structurally modified ascaroside as described in any one of embodiments 1 to 26, a physically modified ascaroside as described in any one of embodiments 27 to 41, or a composition as described in any one of embodiments 42 to 48, wherein the ascaroside or composition is effective in increasing the resistance of the plant to one or more pathogens and / or inducing an immune response in the plant or a part thereof.

[0100] Embodiment 50: The method of Embodiment 49, wherein the part thereof is selected from the group consisting of roots, stems, leaves, seeds and flowers.

[0101] Embodiment 51: The method of Embodiment 49 or Embodiment 50, wherein the plant is a vegetable or fruit plant.

[0102] By reading the following specific embodiments and the accompanying drawings briefly described below, these and other features, aspects and advantages of the present disclosure will be understood. The present invention includes any combination of two, three, four or more of the above-mentioned embodiments and any two, three, four or more features or the combination of elements set forth in the present disclosure, regardless of whether these features or elements are clearly combined in the specific embodiment description of this paper. The present disclosure is intended to be read in an integral manner, so that any separable features or elements (in any one of its various aspects and embodiments) of the disclosed invention should be considered as intended to be combinable, unless the context clearly indicates otherwise. Other aspects and advantages of the present disclosure can be understood from the following.

[0103] definition

[0104] In order to make the present disclosure more easily understood, certain terms will first be defined below. Additional definitions of the following terms and other terms are set forth throughout the specification.

[0105] In this application, unless the context clearly indicates otherwise, the terms "a" and "an" may be understood to mean "at least one". As used in this application, the term "or" may be understood to mean "and / or". In this application, the terms "comprising" and "including" may be understood to cover the listed components or steps, either alone or with one or more additional components or steps. As used in this application, the term "comprise" and variations thereof, such as "comprising" and "comprises" are not intended to exclude other additives, components, integers or steps.

[0106] About, approximately: As used herein, the terms "about" and "approximately" are used as equivalents. Unless otherwise specified, the terms "about" and "approximately" can be understood to allow standard variations, as understood by those of ordinary skill in the art. If a range is provided herein, endpoints are included. Any numeral with or without about / approximately used in this application is intended to cover any normal fluctuations understood by those of ordinary skill in the relevant art. In some embodiments, the term "about" or "approximately" refers to a numerical range falling within 25%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% or less in either direction (greater than or less than) of the reference value, unless otherwise specified or apparent from the context (unless the numeral exceeds 100% of the possible value).

[0107] The definitions of specific functional groups and chemical terms are described in more detail below. For purposes of the present invention, chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th edition, inside cover, and specific functional groups are generally defined as described therein. In addition, the general principles of organic chemistry as well as specific functional moieties and reactivities are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March March's Advanced Organic Chemistry, 5th edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3rd edition, Cambridge University Press, Cambridge, 1987; each of which is incorporated herein by reference in its entirety.

[0108] Certain compounds provided herein may contain one or more asymmetric centers and therefore may exist in various stereoisomeric forms, for example, enantiomers and / or diastereomers. Therefore, the compounds of the present invention and compositions thereof may be in the form of individual enantiomers, diastereomers or geometric isomers, or in the form of a mixture of stereoisomers. In certain embodiments, the compounds described herein are enantiomerically pure compounds. In certain other embodiments, a mixture of enantiomers or diastereomers is provided.

[0109] In addition, certain compounds as described herein may have one or more double bonds, which may exist as Z or E isomers unless otherwise indicated. Compounds may be provided as individual isomers substantially free of other isomers, or as mixtures of various isomers (e.g., racemic mixtures of enantiomers).

[0110] As used herein, the term "isomer" includes any and all geometric isomers and stereoisomers. For example, "isomer" includes cis and trans isomers, E- and Z-isomers, R- and S-enantiomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof as fall within the scope of the present disclosure. For example, in some embodiments, a compound may be provided that is substantially free of one or more corresponding stereoisomers, and it may also be referred to as "stereochemically enriched".

[0111] When a particular enantiomer is preferred, in some embodiments, the enantiomer may be substantially free of the opposite enantiomer, also referred to as "optically enriched". As used herein, "optically enriched" means that the compound consists of one enantiomer, and the ratio is significantly increased. In certain embodiments, the compound is composed of at least about 90% by weight of the enantiomer. In some embodiments, the compound is composed of at least about 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9% by weight of the enantiomer. In some embodiments, the enantiomeric excess of the provided compound is at least about 90%, 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9%. In some embodiments, enantiomers can be separated from the racemic mixture by any method known to those skilled in the art, including chiral high pressure liquid chromatography (HPLC) and the formation and crystallization of chiral salts, or prepared by asymmetric synthesis. See, for example, Jacques et al., Enantiomers, Racemates and Resolutions (Wiley Interscience, New York, 1981); Wilen, SH et al., Tetrahedron 33: 2725 (1977); Eliel, EL Stereochemistry of Carbon Compounds (McGraw-Hill, NY, 1962); Wilen, SH Tables of Resolving Agents and Optical Resolutions p. 268 (EL Eliel, Univ. of Notre Dame Press, Notre Dame, IN 1972).

[0112] As used herein, the terms "halo" and "halogen" refer to an atom selected from fluorine (F, —F), chlorine (Cl, —Cl), bromine (Br, —Br), and iodine (I, —I).

[0113] As used herein, the term "aliphatic" or "aliphatic group" means a hydrocarbon portion that may be straight chain (i.e., unbranched), branched, or cyclic (including fused, bridged, and spiro-fused polycyclics) and may be fully saturated or may contain one or more unsaturated units but is not aromatic. Unless otherwise specified, an aliphatic group contains 1–30 carbon atoms. In certain embodiments, an aliphatic group contains 1-12 carbon atoms. In certain embodiments, an aliphatic group contains 1-8 carbon atoms. In certain embodiments, an aliphatic group contains 1-6 carbon atoms. In some embodiments, an aliphatic group contains 1-5 carbon atoms, in some embodiments, an aliphatic group contains 1-4 carbon atoms, in other embodiments, an aliphatic group contains 1-3 carbon atoms, and in other embodiments, an aliphatic group contains 1-2 carbon atoms. Suitable aliphatic groups include, but are not limited to, straight or branched alkyl, alkenyl, and alkynyl groups and mixtures thereof such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, or (cycloalkyl)alkenyl.

[0114] As used herein, the term "heteroaliphatic" or "heteroaliphatic group" refers to an aliphatic group in which one or more carbon or hydrogen atoms are replaced by a heteroatom (eg, oxygen, nitrogen, sulfur, phosphorus, boron, etc.).

[0115] As used herein, the term "unsaturated" means a moiety having one or more double or triple bonds.

[0116] The term "alkyl" as used herein refers to a saturated, straight or branched hydrocarbon group derived from an aliphatic portion containing one to six carbon atoms by removing a single hydrogen atom. Unless otherwise specified, an alkyl group contains 1-12 carbon atoms. In certain embodiments, an alkyl group contains 1-8 carbon atoms. In certain embodiments, an alkyl group contains 1-6 carbon atoms. In some embodiments, an alkyl group contains 1-5 carbon atoms, in some embodiments, an alkyl group contains 1-4 carbon atoms, in other embodiments, an alkyl group contains 1-3 carbon atoms, and in other embodiments, an alkyl group contains 1-2 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, sec-pentyl, isopentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, etc.

[0117] The term "alkenyl" as used herein means a monovalent group derived from a straight or branched aliphatic moiety, wherein the alkenyl group has at least one carbon-carbon double bond by removing a single hydrogen atom. Unless otherwise specified, an alkenyl group contains 2-12 carbon atoms. In certain embodiments, an alkenyl group contains 2-8 carbon atoms. In certain embodiments, an alkenyl group contains 2-6 carbon atoms. In some embodiments, an alkenyl group contains 2-5 carbon atoms, in some embodiments, an alkenyl group contains 2-4 carbon atoms, in other embodiments, an alkenyl group contains 2-3 carbon atoms, and in other embodiments, an alkenyl group contains 2 carbon atoms. An alkenyl group includes, for example, vinyl, propenyl, butenyl, 1-methyl-2-butene-1-yl, etc.

[0118] The term "aryl", used alone or as part of a larger moiety in "aralkyl", "aralkyloxy", or "aryloxyalkyl", refers to monocyclic and polycyclic ring systems having a total of 5 to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members. The term "aryl" can be used interchangeably with the term "aromatic ring". In certain embodiments, "aryl" refers to an aromatic ring system including, but not limited to, phenyl, biphenyl, naphthyl, anthracenyl, etc., which may carry one or more substituents. Also included within the scope of the term "aryl", as used herein, are groups in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimido, or tetrahydronaphthyl, etc.

[0119] As described herein, compounds as provided herein may contain "optionally substituted" moieties. In general, whether or not the term "optionally" is added in front, the term "substituted" means that one or more hydrogens of the specified part are replaced by suitable substituents. Unless otherwise specified, the "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in a given structure can be substituted by more than one substituent selected from a specified group, the substituent may be the same or different at each position. The combination of substituents envisioned is preferably a combination of stable or chemically feasible compounds. The term "stable" as used herein refers to a compound that is substantially unchanged when subjected to conditions that allow compound preparation, detection, and in certain embodiments, its recovery, purification, and use for one or more purposes disclosed herein.

[0120] Suitable monovalent substituents on the substitutable carbon atoms of the "optionally substituted" group are independently halogen; -(CH2) 0–4 R o ; –(CH2) 0–4 OR o ; -O-(CH2) 0-4 C(O)OR o; –(CH2) 0–4 CH(OR o )2; –(CH2) 0–4 SR o ; –(CH2) 0–4 Ph, it can be R o Substitution; –(CH2) 0–4 O(CH2) 0–1 Ph, it can be R o Substitution; –CH=CHPh, which can be replaced by R o Substitution; –NO2; –CN; –N3; –(CH2) 0–4 N(R o )2; –(CH2) 0–4 N(R o )C(O)R o ; –N(R o )C(S)R o ; –(CH2) 0-4 N(R o )C(O)NR o 2; –N(R o )C(S)NR o 2; –(CH2) 0–4 N(R o )C(O)OR o ;-N(R o )N(R o )C(O)R o ; –N(R o )N(R o )C(O)NR o 2; –N(R o )N(R o )C(O)OR o ; –(CH2) 0–4 C(O)R o ;-C(S)R o ; –(CH2) 0–4 C(O)OR o ; –(CH2) 0–4 C(O)N(R o )2; –(CH2) 0–4 C(O)SR o ; –(CH2) 0–4 C(O)OSiR o 3; –(CH2) 0–4 OC(O)R o ; –OC(O)(CH2) 0–4 SR–, SC(S)SR o ; –(CH2) 0–4SC(O)R o ; –(CH2) 0–4 C(O)NR o 2; -C(S)NR o 2; –C(S)SR o ; –SC(S)SR o 、–(CH2) 0–4 OC(O)NR o 2; –C(O)N(OR o )R o ; –C(O)C(O)R o ; -C(O)CH2C(O)R o ; –C(NOR o )R o ; –(CH2) 0–4 SSR o ; -(CH2) 0–4 S(O)2R o ; –(CH2) 0–4 S(O)2OR o ; -(CH2) 0–4 OS(O)2R o ; –S(O)2NR o 2; –(CH2) 0–4 S(O)R o ; –N(R o )S(O)2NR o 2; –N(R o )S(O)2R o ;-N(OR o )R o ; –C(NH)NR o 2; –P(O)2R o ; –P(O)R o 2;–OP(O)R o 2;–OP(O)(OR o )2;SiR o 3;–(C 1–4 Straight or branched alkylene)O–N(R o )2; or – (C 1–4 Straight or branched alkylene) C(O)O–N(R o )2, where each R o may be substituted as defined below and are independently hydrogen, C 1-8 Aliphatic, –CH2Ph, –O(CH2) 0–1 Ph or a 5-6 membered saturated, partially unsaturated or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, or, notwithstanding the definitions given above, two independent occurrences of Ro Together with their intervening atoms they form a 3-12 membered saturated, partially unsaturated or aromatic monocyclic or polycyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, said ring may be substituted as defined below.

[0121] In R o (or two independent occurrences of R o Suitable monovalent substituents on the ring formed together with their intervening atoms are independently halogen, –(CH2) 0–2 R · 、–(halogenated R · ),–(CH2) 0–2 OH, –(CH2) 0–2 OR · 、–(CH2) 0–2 CH(OR · )2; -O(halogenated R · )、–CN、–N3、–(CH2) 0–2 C(O)R · 、–(CH2) 0–2 C(O)OH, –(CH2) 0–2 C(O)OR · 、-(CH2) 0-4 C(O)N(R o )2; –(CH2) 0–2 SR · 、–(CH2) 0–2 SH, –(CH2) 0–2 NH2, –(CH2) 0–2 NHR · 、-(CH2) 0-2 NR · 2. –NO2, –SiR · 3. –OSiR · 3. –C(O)SR · ,–(C 1–4 Straight or branched alkylene)C(O)OR · or –SSR · , where each R · is unsubstituted or, when preceded by "halo", is substituted only by one or more halogens, and is independently selected from C 1–4 Aliphatic, -CH2Ph, –O(CH2) 0–1 Ph or a 5-6 membered saturated, partially unsaturated or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur. o Suitable divalent substituents on a saturated carbon atom of include =0 and =S.

[0122] Suitable divalent substituents on a saturated carbon atom of an "optionally substituted" group include the following: =0, =S, =NNR * 2. =NNHC(O)R * 、=NNHC(O)OR * 、=NNHS(O)2R * , =NR * , =NOR * , –O(C(R * 2)) 2–3 O–or–S(C(R * 2)) 2–3 S–, where each independent occurrence of R * Selected from hydrogen, C 1–6 an aliphatic group (which may be substituted as defined below) or an unsubstituted 5-6 membered saturated, partially unsaturated or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur. Suitable divalent substituents attached to an adjacent substitutable carbon of an "optionally substituted" group include: -O(CR * 2) 2–3 O–, where each independent occurrence of R * is selected from hydrogen, C which may be substituted as defined below 1–6 aliphatic, or an unsubstituted 5-6 membered saturated, partially unsaturated or aromatic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur.

[0123] R * Suitable substituents on the aliphatic group include halogen, -R · 、-(halogenated R · ), –OH, –OR · 、–O(halogenated R · ), –CN, –C(O)OH, –C(O)OR · , –NH2, –NHR · ,–NR · 2 or –NO2, where each R · is unsubstituted or, when preceded by "halo", is substituted only by one or more halogens, and is independently C 1–4 Aliphatic, –CH2Ph, –O(CH2) 0– 1Ph or a 5-6 membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur.

[0124] Suitable substituents on a substitutable nitrogen of an "optionally substituted" group include or Each of these are independently hydrogen, substituted C 1–6 aliphatic, unsubstituted -OPh or an unsubstituted 5-6 membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, or, notwithstanding the definitions given above, two independent occurrences of Together with their intervening atom(s), they form a 3-12 membered saturated, partially unsaturated or aromatic monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur.

[0125] Suitable substituents on the aliphatic group are independently halogen, -R · 、-(halogenated R · ), –OH, –OR · 、–O(halogenated R · ), –CN, –C(O)OH, –C(O)OR · , –NH2, –NHR · ,–NR · 2 or -NO2, where each R · is unsubstituted or, when preceded by "halo", is substituted only by one or more halogens, and is independently C 1–4 Aliphatic, –CH2Ph, –O(CH2) 0–1 Ph or a 5-6 membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur.

[0126] As used herein, the term "substantially" refers to the qualitative condition of exhibiting a full or nearly full degree or extent of a characteristic or property of interest.

[0127] A convention of naming ascarosides using a prefix of several letters followed by a pound sign (#) and a number is sometimes used (e.g., ascr#18). This convention is used in the scientific literature, and one skilled in the art will understand that each such name is associated with a specific chemical structure of known composition, and will readily understand the structure of the molecule referred to using this naming convention. Unless otherwise indicated, all compound identifiers in this format used herein are in accordance with the C. elegans Small Molecule Identifier Database (SMID-DB) (maintained at: http: / / www.smid-db.org ) as described in .

[0128] The term "pathogen" refers to any bacterium, fungus, oomycete, virus, nematode (eg, cyst nematode or root knot nematode), or insect that is pathogenic to plants. BRIEF DESCRIPTION OF THE DRAWINGS

[0129] In the drawings, features are not necessarily represented to scale, but rather generally focus on illustrating the principles of the disclosed compositions and methods and are not intended to be limiting. For clarity, not every component may be labeled in the drawings. In the following description, various embodiments will be described with reference to the following drawings, in which:

[0130] Figure 1A , 1B , 1C and 1D are non-limiting representations of examples of ascaroside oligomers according to certain embodiments of the present disclosure;

[0131] Figure 2 is a non-limiting representation of an oligomer or polymer modified ascaroside comprising an ester linkage between adjacent ascaroside moieties;

[0132] Figure 3A and 3B is a non-limiting representation of examples of dimeric ascarosides without a linker in the middle;

[0133] Figure 4A , 4B and 4C are non-limiting representations of ascaroside moieties comprising one, two, and three polymer arms, respectively; and

[0134] Figure 5 is a non-limiting representation of a polymer comprising pendant ascaroside moieties. DETAILED DESCRIPTION

[0135] Compounds, compositions and methods for timed release of ascarosides are provided. The present disclosure relates to delivery of ascarosides or derivatives thereof by modified release characteristics. The modified release characteristics can be, for example, extended, delayed and / or controlled release for maintaining effective concentrations of ascarosides or derivatives thereof over an extended period of time. Some such modified release characteristics can be provided by structural modification of ascarosides (or derivatives thereof) such that the desired ascaroside molecules or derivatives thereof are released from the modified compositions over time and / or under certain environmental exposures / triggers. Some such modified release characteristics can be provided by composition-based methods such that the desired ascaroside molecules or derivatives thereof are released based on degradation of the composition containing them.

[0136] Ascarosides are secondary metabolites produced by nematodes. A large number of structurally diverse ascarosides have been found in nature, and these molecules are thought to function as an evolutionarily conserved chemical language that nematodes use to control multiple aspects of their development. Ascarosides are also sensed by other organisms and have been shown to have a range of effects on a variety of organisms including bacteria, fungi, plants, and mammals, including humans.

[0137] Ascarosides are derivatives of ascarylose, a dideoxy sugar lacking hydroxyl groups at positions 3 and 6. Ascarosides have the general structure shown in Formula I:

[0138]

[0139] in:

[0140] Z is an optionally substituted C 2-40 an aliphatic group, and

[0141] R a and R b Each of which is independently -H, or an optionally substituted moiety selected from the group consisting of: C 1-20 Aliphatic group, C 1-20 Acyl, C 1-20 Heteroaliphatic, aryl, heteroaryl, hydroxyl protecting group, phosphorus-linked functional group, sulfur-linked functional group, silicon-linked functional group, C 2-20 Carbonate (e.g. part -C(O)OR c ), C 2-20 Carbamate (e.g., part -C(O)N(R c )2) C 2-20 Thioesters (e.g., moieties -C(S)R c ), C 2-20 Thiocarbonates (e.g., moieties -C(S)OR c ), C 2-20 Dithiocarbonates (e.g., part-C(S)SR c ), C 1-20 Thiocarbamates (e.g., moieties -C(S)N(R c ) 2), a sugar moiety, a peptide, a polymer chain, or a linker to another ascaroside molecule via a bond or a carbon-containing linker. c is independently selected at each occurrence from -H, optionally substituted C 1-12 aliphatic, optionally substituted C 1-12 heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, a polymer chain, or a linker to another ascaroside molecule via a bond or a carbon-containing linker, and wherein R a and R b Together they may form an optionally substituted ring, optionally containing one or more heteroatoms, and optionally containing one or more sites of unsaturation.

[0142] In certain embodiments, Z is:

[0143] (i) –CH(CH3)–R 1 , where R 1 is an optionally substituted C 1-40Aliphatic group

[0144] (ii) –CH(CH3)–(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0145] (iii) –CH(CH3)–(CH2) n –CH=CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0146] (iv) –CH(CH3)–(CH2) n –CH(OH)–CH-CO2R 32 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0147] (v) –CH(CH3)–(CH2) n –C(O)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0148] (vi)–(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0149] (vii)–(CH2) n –CH=CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0150] (viii)–(CH2) n –CH(OH)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; or

[0151] (ix)–(CH2) n –C(O)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 heteroaliphatic groups, optionally substituted aromatic groups, optionally substituted heteroaryl groups, glycosides, amino acids, peptides, nucleotides, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety.

[0152] In certain embodiments, Z is:

[0153] (x)–CH(CH3)–(CH2) n –CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0154] (xi)–CH(CH3)–(CH2) n –CH=CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0155] (xii)–CH(CH3)–(CH2) n –CH(OH)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0156] (xiii) –CH(CH3)–(CH2) n –C(O)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0157] (xiv)–(CH2) n –CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0158] (xv)–(CH2) n –CH=CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety;

[0159] (xvi)–(CH2) n –CH(OH)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; or

[0160] (xvii)–(CH2) n –C(O)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety.

[0161] In certain embodiments, R a Yes -H.

[0162] In certain embodiments, R b Yes -H.

[0163] In certain embodiments, R a and R b In certain embodiments, R a and R b All are -H.

[0164] In certain embodiments, R a and R b In certain embodiments, R a Yes -H, and R bis a group other than -H. In certain embodiments, R a is a group other than -H and R b is -H. In certain embodiments, R a Yes -H and R b is a paraben. In certain embodiments, R a Yes -H and R b is indole-3-carboxylate. In certain embodiments, R a Yes -H and R b is (E)-2-methyl-2-butenoate. In certain embodiments, R a Yes -H and R b is a picolinate. In certain embodiments, R a Yes -H and R b In certain embodiments, R a Yes -H and R b is (R)-2-hydroxy-2-(4-hydroxyphenyl)ethyl)amino)-4-oxobutanoate. In certain embodiments, R a Yes -H and R b It is 4-((4-hydroxyphenethyl)amino)-4-oxobutanoate.

[0165] In certain embodiments, R a and R b are all -H, and Z is selected from the formulae defined in (i) to (ix) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (i) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (ii) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (iii) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (iv) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (v) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (vi) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (vii) above. In certain embodiments, R a and R bare -H, and Z conforms to formula (viii) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (ix) above. In certain embodiments, R a and R b are -H, and Z conforms to Formula (x) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (xi) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (xii) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (xiii) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (xiv) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (xv) above. In certain embodiments, R a and R b are -H, and Z conforms to formula (xvi) above. In certain embodiments, R a and R b All are -H, and Z conforms to formula (xvii) above.

[0166] In certain embodiments, R 2 is -H. In certain embodiments, R 2 is a metal cation. In certain embodiments, R 2 is an organic cation (e.g., a nitrogen or phosphorus-centered cationic group). 2 is an optionally substituted C 1-20 In certain embodiments, R 2 is an optionally substituted C 1-12 In certain embodiments, R 2 is an optionally substituted C 1-8 In certain embodiments, R 2 is an optionally substituted C 1-6 In certain embodiments, R 2 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. 2 is an optionally substituted aromatic group. In certain embodiments, R 2 is a glycoside. In certain embodiments, R 2In certain embodiments, R 2 In certain embodiments, R 2 Contains nucleotides.

[0167] In certain embodiments, at least one R 3 is -H. In certain embodiments, both R 3 The group is -H. In certain embodiments, at least one R 3 is an optionally substituted C 1-20 In certain embodiments, two R 3 The group is an optionally substituted C 1-20 aliphatic groups, which may be the same or different. In certain embodiments, at least one R 3 is an optionally substituted C 1-12 In certain embodiments, at least one R 3 is an optionally substituted C 1-8 In certain embodiments, at least one R 3 is an optionally substituted C 1-6 In certain embodiments, at least one R 3 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. 3 is -CH2CH2OH. In certain embodiments, at least one R 3 Yes -CH2CH2OR 2 , where R 2 As defined in the genus and subgenus herein. In certain embodiments, at least one R 3 is an optionally substituted aromatic group. In certain embodiments, at least one R 3 In certain embodiments, at least one R 3 In certain embodiments, at least one R 3 At least one R 3 In certain embodiments, at least one R 3 Contains nucleotides.

[0168] In certain embodiments, the ascaroside is selected from the group consisting of:

[0169]

[0170] Where x is an integer from 1 to 22, and R a , R b and R 2 Each of which is as defined above and in the genera and subgenera herein.

[0171] In certain embodiments, the ascaroside is selected from the group consisting of:

[0172]

[0173] Where x, R a and R b Each of which is as defined above and in the genera and subgenera herein.

[0174] In certain embodiments, the ascaroside is selected from the group consisting of:

[0175]

[0176] Where y is an integer from 1 to 20, and R a , R b and R 2 Each of which is as defined above and in the genera and subgenera herein.

[0177] In certain embodiments, the ascaroside is selected from the group consisting of:

[0178]

[0179] Where y, R a and R b Each of which is as defined above and in the genera and subgenera herein.

[0180] In certain embodiments, the ascaroside is selected from the group consisting of:

[0181]

[0182] Where x is an integer from 1 to 22, and R 2 As defined above and in the genus and subgenera herein.

[0183] In certain embodiments, the ascaroside is selected from the group consisting of:

[0184]

[0185] wherein x is as defined above and in the genera and subgenera herein.

[0186] In certain embodiments, the ascaroside is selected from the group consisting of:

[0187]

[0188] Where y is an integer from 1 to 20, and R 2 As defined above and in the genus and subgenera herein.

[0189] In certain embodiments, the ascaroside is selected from the group consisting of:

[0190]

[0191] wherein y is as defined above and in the genus and subgenera herein.

[0192] In certain embodiments, the ascaroside is selected from the group consisting of:

[0193]

[0194] Where x is an integer from 1 to 22, and R a , R b and R 3 Each of which is as defined above and in the genera and subgenera herein.

[0195] In certain embodiments, the ascaroside is selected from the group consisting of:

[0196]

[0197] where x and R 3 Each of which is as defined above and in the genera and subgenera herein.

[0198] In certain embodiments, the ascaroside is selected from the group consisting of:

[0199]

[0200] Where y is an integer from 1 to 20, and R a , R b and R 2 Each of which is as defined above and in the genera and subgenera herein.

[0201] In certain embodiments, the ascaroside is selected from the group consisting of:

[0202]

[0203] where y and R 3 Each of which is as defined above and in the genera and subgenera herein.

[0204] In certain embodiments, x in any of the structures herein is an integer between 2 and 18, inclusive. In certain embodiments, x in any of the structures herein is an integer between 4 and 10, inclusive. In certain embodiments, x in any of the structures herein is an integer between 6 and 12, inclusive. In certain embodiments, x in any of the structures herein is an integer between 5 and 9, inclusive. In certain embodiments, x in any of the structures herein is 7, 8, or 9. In certain embodiments, x in any of the structures herein is 6. In certain embodiments, x in any of the structures herein is 7. In certain embodiments, x in any of the structures herein is 8. In certain embodiments, x in any of the structures herein is 9. In certain embodiments, x in any of the structures herein is 10. In certain embodiments, x in any of the structures herein is 11. In certain embodiments, x in any of the structures herein is 12.

[0205] In certain embodiments, x in any of the structures herein is an integer greater than 5. In certain embodiments, x in any of the structures herein is an integer greater than 6, greater than 7, greater than 9, or greater than 10. In certain embodiments, x in any of the structures herein is an integer between 10 and 20.

[0206] In certain embodiments, provided modified ascarosides may include a mixture of ascarosides that differ only in the value of x (i.e., the modified ascarosides include a mixture of congeners with different side chain lengths). In certain embodiments, such modified ascarosides are characterized in that the average value of x in the modified ascarosides is between about 2 and about 20. In certain embodiments, such modified ascarosides are characterized in that the average value of x in the composition is between about 3 and about 10, between about 4 and about 12, between about 6 and about 10, or between about 7 and about 9. In certain embodiments, such modified ascarosides are characterized in that the average value of x is greater than about 4, greater than about 5, greater than about 6, greater than about 7, or greater than about 8. The average value of x in such modified ascarosides can be determined by various methods well known in the art, including, but not limited to, by 1 The mixture can be analyzed by H NMR spectroscopy, mass spectrometry, high performance liquid chromatography, and the like.

[0207] In certain embodiments, y in any of the structures herein is an integer between 2 and 18, inclusive. In certain embodiments, y in any of the structures herein is an integer between 4 and 10, inclusive. In certain embodiments, y in any of the structures herein is an integer between 6 and 12, inclusive. In certain embodiments, y in any of the structures herein is an integer between 5 and 9, inclusive. In certain embodiments, y in any of the structures herein is 7, 8, or 9. In certain embodiments, y in any of the structures herein is 6. In certain embodiments, y in any of the structures herein is 7. In certain embodiments, y in any of the structures herein is 8. In certain embodiments, y in any of the structures herein is 9. In certain embodiments, y in any of the structures herein is 10. In certain embodiments, y in any of the structures herein is 11. In certain embodiments, y in any of the structures herein is 12.

[0208] In certain embodiments, y in any of the structures herein is an integer greater than 5. In certain embodiments, y in any of the structures herein is an integer greater than 6, greater than 7, greater than 9, or greater than 10. In certain embodiments, y in any of the structures herein is an integer between 10 and 20.

[0209] In certain embodiments, provided modified ascarosides may include a mixture of ascarosides that differ only in the value of y (i.e., the modified ascarosides include a mixture of congeners having different side chain lengths). In certain embodiments, such modified ascarosides are characterized by an average value of y between about 2 and about 20. In certain embodiments, such modified ascarosides are characterized by an average value of y in the composition between about 3 and about 10, between about 4 and about 12, between about 6 and about 10, or between about 7 and about 9. In certain embodiments, such modified ascarosides are characterized by an average value of y greater than about 4, greater than about 5, greater than about 6, greater than about 7, or greater than about 8. The average value of y in such modified ascarosides can be determined by various methods well known in the art, including, but not limited to, by 1 The mixture can be analyzed by H NMR spectroscopy, mass spectrometry, high performance liquid chromatography, and the like.

[0210] In one embodiment, the ascarosides useful in the present invention have the general structure (I), wherein Z is -CH(CH3)-(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide.

[0211] In one embodiment, the ascarosides useful in the present invention have the general structure (I), wherein Z is -CH(CH3)-(CH2) n –CH=CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide.

[0212] Specific ascarosides useful in the present invention include, but are not limited to, ascr#7 and ascr#18.

[0213]

[0214] In certain embodiments, the ascarosides used in the provided methods are selected from the group consisting of ascr#9, ascr#12, ascr#14, ascr#1, ascr#10, ascr#16, ascr#18, ascr#20, ascr#22, ascr#24, ascr#26, ascr#28, ascr#30, ascr#32, ascr#34, and ascr#36. In certain embodiments, the ascarosides used in the provided methods are selected from the group consisting of ascr#10, ascr#16, ascr#18, ascr#20, ascr#22, and ascr#24. In certain embodiments, the ascarosides used in the provided methods are selected from the group consisting of ascr#9, ascr#14, ascr#10, and ascr#18.

[0215] In certain embodiments, the ascaroside used in the provided methods is selected from the group consisting of ascr#5, oscr#9, oscr#12, oscr#1, oscr#14, oscr#10, oscr#16, oscr#18, oscr#20, oscr#22, oscr#24, oscr#26, oscr#28, oscr#30, oscr#32, oscr#34, and oscr#36. In certain embodiments, the ascaroside used in the provided methods is selected from the group consisting of oscr#10, oscr#16, oscr#18, oscr#20, and oscr#22. In certain embodiments, the ascaroside used in the provided methods is selected from the group consisting of bhas#5, oscr#9, oscr#12, oscr#1, oscr#14, oscr#10, oscr#16, oscr#18, oscr#20, oscr#22, oscr#24, oscr#26, oscr#28, oscr#30, oscr#32, oscr#34, and oscr#36. In certain embodiments, the ascaroside used in the provided methods is selected from the group consisting of oscr#10, oscr#16, oscr#18, oscr#20, and oscr#22.

[0216] In certain embodiments, the ascaroside used in the provided methods is selected from the group consisting of bhas#9, bhas#10, bhas#16, bhas#18, bhas#22, bhas#24, bhas#26, bhas#28, bhas#30, bhas#32, bhas#34, bhas#36, bhas#38, bhas#40, and bhas#42.

[0217] In certain embodiments, the ascaroside used in the provided methods is selected from the group consisting of bhos#10, bhos#16, bhos#18, bhos#22, bhos#24, bhos#26, bhos#28, bhos#30, bhos#32, bhos#34, bhos#36, bhos#38, bhos#40, and bhos#42.

[0218] In certain embodiments, the ascaroside used in the provided methods is selected from the group consisting of ascr#18, oscr#16, oscr#17, oscr#15, bhas#18, bhos#16, glas#18, dhas#18, ibha#18, ibho#16, icas#18, icos#15, icos#16, and any combination of two or more of these.

[0219] Ascarosides can be obtained from natural sources (e.g., nematodes) or prepared synthetically. Ascarosides can be prepared synthetically, for example, by converting 1-O-substituted rhamnose to 1-O-substituted ascarosides. An exemplary method for preparing ascarosides includes: providing 1-O-substituted rhamnose as a raw material; forming a monosulfonate on the 3-OH group of the raw material; and treating the monosulfonate with a hydride source to form a 1-O-substituted ascarosides. In certain embodiments, the formation of the monosulfonate is carried out on a substrate without a hydroxyl protecting group at position 2 or 4 of the rhamnose raw material. In certain embodiments, such methods include contacting the raw material with a sulfonating agent (i.e., a sulfonyl halide, a sulfonic anhydride, or a similar reagent) in the presence of a Lewis acid. Specific details about the synthesis of 1-O-substituted ascarosides can be found in PCT application PCT / IB2021 / 056981, which is incorporated herein by reference.

[0220] Structurally modified ascarosides

[0221] As described above, in some embodiments of the present disclosure, ascaroside molecules are modified to provide compounds that undergo modified release of ascaroside molecules during use (e.g., when applied to a plant, animal, or an environment surrounding a plant or animal). Some such structurally modified ascarosides include oligomers or polymers composed at least in part of ascarosides. In some embodiments, the structural modification is generally reversible, i.e., the structurally modified ascaroside can release one or more ascaroside molecules upon one or more environmental exposures / triggers or upon degradation.

[0222] In some embodiments, the structurally modified ascaroside is an ascaroside-based oligomer or polymer, including oligomers (e.g., dimers, trimers, tetramers, etc.) or polymers (i.e., comprising repeating units containing ascarosides) of ascarosides. The oligomer or polymer may comprise two or more linked ascarosides having the same chemical formula and / or may comprise two or more linked ascarosides having different chemical formulas. In some embodiments, the ascaroside molecules are directly linked to each other via covalent bonds between functional groups already present on the ascaroside molecules. For example, in some embodiments, such structurally modified ascarosides may comprise an ester bond, which may be formed by a carboxylic acid on the side chain of one ascaroside (e.g., present in some embodiments as a component of the "Z" group in Formula (I) above) to a hydroxyl functional group on another ascaroside molecule (e.g., wherein R of Formula (I) is present). a or R b is H, or where the ascaroside further comprises an OH substituent (e.g., where the Z group of formula (I) comprises an OH substituent). In some embodiments, the ascaroside molecules are indirectly linked to each other via covalent bonds between the multivalent linker and the functional groups present on the ascaroside molecules.

[0223] In some embodiments, such ascaroside-based oligomers or polymers include oligomers or polymers consisting essentially of ascaroside molecules (e.g., oligomers or polymers in which ascaroside comprises the majority monomer that makes up the oligomer or polymer). In other embodiments, such compositions comprise copolymers or co-oligomers of ascaroside molecules with multivalent linkers or other monomers.

[0224] In certain embodiments, provided ascaroside-based oligomers or polymers conform to formula (II):

[0225] A-[(L) m -A] p or L-[A-(L) m ] p (Formula II),

[0226] wherein each A is independently an ascaroside molecule; L is a multivalent linker moiety covalently bound to A, m is 0 or 1, and p is an integer between 1 and 1000. In some embodiments, the oligomer or polymer comprises a covalent bond to a carboxylic acid functional group on A (e.g., via an ester bond or an amide bond). In some embodiments, the oligomer or polymer comprises a covalent bond to a hydroxyl functional group on A (e.g., via an ether bond, an ester bond, a glycosidic bond, a urethane bond, a carbonate bond, or a siloxane bond). Thus, the composition of the optional multivalent linker L can vary widely.

[0227] In certain embodiments, provided ascaroside-based oligomers or polymers conform to formula (III):

[0228] [(L) m -A] p or [A-(L) m ] p (Formula III),

[0229] wherein each A is independently an ascaroside molecule; L is a multivalent linker moiety covalently bound to A, m is 0 or 1, and p is an integer between 1 and 1000. In some embodiments, the oligomer or polymer comprises a covalent bond to a carboxylic acid functional group on A (e.g., via an ester bond or an amide bond). In some embodiments, the oligomer or polymer comprises a covalent bond to a hydroxyl functional group on A (e.g., via an ether bond, an ester bond, a glycosidic bond, a urethane bond, a carbonate bond, or a siloxane bond). Thus, the composition of the optional multivalent linker L can vary widely.

[0230] Such ascaroside-based oligomers and polymers provided according to the present disclosure may be linear or branched. Figure 1A Certain non-limiting examples of oligomers containing five linked ascaroside ("A") moieties are shown, wherein each of A1, A2, A3, A4, and A5 and all "L" groups can be the same or different. Each "a" is an integer of 0 or 1, i.e., each A can be directly linked to an adjacent A by a bond or can contain a linker (L) therebetween. It should be understood that for modified ascarosides in other oligomer and polymer forms, each linkage between ascaroside moieties can form a linear or branched portion of the respective oligomer or polymer, depending on, for example, the point of attachment between an ascaroside moiety and an adjacent ascaroside moiety or between an ascaroside moiety and L.

[0231] In some embodiments, such ascaroside-based oligomers or polymers may comprise ester bonds between adjacent ascaroside moieties. Non-limiting representative structures of oligomers or polymer-modified ascarosides comprising such ester bonds are as follows: Figure 2 As shown, wherein A' refers to the part of the ascaroside molecule not explicitly shown in the figure (i.e., comprising a tetrahydropyranyl ring and OR a -、OR b- and / or at least a portion (or all) of OZ substituents), wherein each A' may be the same or different, and wherein p is an integer from 1 to 1000. Oligomers and polymers within the scope of the present disclosure may be linear (e.g., wherein all A'-containing subunits are connected to at most two adjacent subunits) or may be branched (e.g., wherein at least some of the A'-containing subunits are directly or through a linker connected to more than two adjacent A subunits). In some embodiments, except for the terminal A' subunit, each A' is connected to two additional A' subunits by an ester bond. In some embodiments, except for the terminal A' subunit, at least some of the A' subunits are connected to three additional A' subunits.

[0232] Chemical reactions that can be suitably used to produce oligomers and polymers from molecules containing hydroxyl groups and / or carboxylic acids are well known in the art and can be readily adapted to provide oligomers or polymers comprising ascaroside. For example, catalysts, methods, and processing techniques that can be employed are described in Textbook of Polymer Science, 3rd edition, Fred W. Billmeyer, ed. (ISBN: 978-0-471-03196-3), which is incorporated herein by reference in its entirety. Depending on the target oligomer or polymer structure, it may be desirable to utilize ascaroside precursors having one or more reactive functional groups masked by protecting groups. In this approach, covalent bonds can be formed with specific functional groups on the ascaroside molecule without the participation or interference of other functional groups. Once the desired oligomer or polymer is formed, such protecting groups can be removed. Suitable protecting groups and strategies for their formation and removal are described in. Greene's Protective Groups in Organic Synthesis , Peter G. M. Wuts and Theodora W. Greene, eds. (ISBN: 9780471697541), which is incorporated herein by reference in its entirety. In certain embodiments, one or more of the hydroxyl groups on the ascarylose of the ascaroside precursor are protected, and the ascaroside precursor oligomerizes by reaction of the carboxylic acid groups (or their reactive derivatives) present on the ascaroside side chains. In certain embodiments, the ascaroside precursor has a masked reactive protecting group for the carboxylic acid groups present on the ascaroside side chains, and the ascaroside precursor oligomerizes by reaction of one or more hydroxyl groups present on the ascarylose.

[0233] In certain embodiments, an ascaryl oligomer or polymer is formed by first reacting an ascaryl sugar or a derivative thereof with an agent that attaches a polymerizable group to the molecule - for example, there are known polymerization processes for polymerizable functional groups such as olefins, amines, isocyanates, epoxides, acyl halides, and the like. Such polymerizable functional groups can be introduced by means well known in the art of synthetic organic chemistry. Methods for incorporating polymerizable functional groups into ascarosides may require the use of protecting groups as described above to ensure that the group is attached at the desired location, or that other functional groups present on the ascaroside do not interfere with the process of attaching the functional group or subsequent processes necessary to form the oligomer or polymer. Such polymerizable functional groups are preferably attached to the ascaroside substrate via a bond that is labile under biological or environmental conditions, so that when the resulting oligomer or polymer degrades, free ascaroside molecules can be released.

[0234] In certain embodiments, the multivalent linker "L" may comprise an oligomer or polymer group (e.g., L may be composed of a chain of repeated monomer subunits). In certain embodiments, L comprises a polyester, a polyamide, a polyether, a polycarbonate, or a polyolefin. In certain embodiments, L comprises a biopolymer. In certain embodiments, L comprises a carbohydrate, a peptide, a protein, RNA, or DNA. In certain embodiments, L comprises a carbohydrate. In certain embodiments, L comprises starch, cellulose, chitosan, or chitin. In certain embodiments, L comprises a peptide or a protein. In certain embodiments, L comprises a polynucleotide.

[0235] Figure 3A and 3B Non-limiting examples of certain specific ascaroside dimers within the scope of the present disclosure are provided (where a=0, i.e., no "L" linker group is present between ascaroside moieties). One skilled in the art will appreciate that each ascaroside can be linked to the adjacent ascaroside by its OZ group (with an OR on the adjacent ascaroside). a OR b Substituent condensation) or through its OR a OR b In certain embodiments, an oligomer is provided in which each ascaroside is linked in the same manner (e.g., the Z group on the first ascaroside is esterified with the carboxyl moiety of the OZ substituent on the adjacent ascaroside). a The Z group on the second ascaroside is esterified with the R group on the third ascaroside. a The Z group on the third ascaroside is esterified with the R group on the fourth ascaroside. a In other embodiments, an oligomer is provided in which each ascaroside is randomly linked (e.g., a Z group on the first ascaroside is linked to an R group on the second ascaroside). a The Z group on the second ascaroside is esterified with the R group on the third ascaroside.b The group is esterified, and the R a group is esterified with the Z group on the fourth ascaroside).

[0236] In some embodiments, the structurally modified ascarosides as provided herein are oligomer-functionalized ascarosides or polymer-functionalized ascarosides, which include ascarosides chemically bonded to natural or synthetic oligomers or polymers. For example, Z, R a and R b Any one or more of can be functionalized with an oligomer or polymer. Three exemplary embodiments are depicted in FIG. 4 , wherein the composition and / or length of each of polymer 1, polymer 2, and polymer 3 can be the same or different, and wherein each of the mentioned polymers can be present or absent in different embodiments (e.g., the molecule can include only one polymer attached to an ascaroside, the molecule can include two polymers attached to different moieties on an ascaroside, or the molecule can include three polymers attached to different moieties on an ascaroside). The polymers can be covalently bonded to the ascaroside in a manner similar to that described above for ascaroside-based oligomers or polymers. Specifically, given the ascaroside structure of formula (I), the pendant polymers can incorporate Z, OR a OR b The polymer functionalized ascaroside may be a linear polymer, a branched polymer, a hyperbranched polymer, a bottle brush polymer, or a dendrimer. The polymer may comprise a single repeating unit, or may be a copolymer (e.g., a block copolymer, a random copolymer, a graft copolymer, a tapered copolymer, or an alternating copolymer). The number of repeating units / length of the oligomer or polymer may vary; in some embodiments, the oligomer or polymer comprises from about two to about one thousand repeating units. The polymer may be natural or synthetic, or may be a mixture of natural polymers or synthetic polymers.

[0237] Suitable polymers include all agriculturally acceptable polymers that can be appropriately functionalized to covalently bind to the moiety present on the ascaroside molecule. In preferred embodiments, such polymers are biodegradable polymers. In some embodiments, such polymers are biobased or natural polymers. In some embodiments, such polymers are synthetic polymers. Some non-limiting examples of suitable polymers include: chitosan, chitin, starch, lignin, agar, pectin, cellulose, other polysaccharides (e.g., bark, sawdust, other cellulose wastes), poly(ethylene glycol), poly(caprolactone), poly(lactide), poly(glycolic acid), polybutene, poly(vinyl alcohol), poly(vinyl chloride), poly(citric acid), poly(acrylate), poly(aspartic acid), poly(ethylene), poly(ethylene vinyl acetate), polyethylene vinyl acetate (PEVA), polystyrene, polydivinylbenzene and their derivatives and copolymers.

[0238] Suitable polymers include pharmaceutically acceptable polymers. Such pharmaceutically acceptable polymers may be appropriately functionalized so as to covalently bind to moieties present on the ascaroside molecule. In preferred embodiments, such polymers are biocompatible polymers and / or metabolically unstable polymers.

[0239] In other embodiments, the structurally modified ascaroside is a polymer with pendant ascarosides, wherein one or more ascarosides are directly or indirectly bonded to the backbone of the polymer as pendant groups, e.g. Figure 5 It is worth noting that Figure 5 In the for simplicity, the polymer is shown as having five pendant ascaroside ("A") groups; however, it should be understood that the present disclosure is not limited thereto; the number of pendant A groups on a given polymer chain can vary within a range, for example, from 2 to about 1,000 in some embodiments. The composition of the polymer varies widely and can be, for example, any of the agriculturally acceptable polymers mentioned above. In certain embodiments, the composition comprises a polymer having pendant hydroxyl or acyloxy groups that can be esterified or transesterified with the carboxyl groups of the ascaroside or modified ascaroside, such as polyvinyl alcohol or polyvinyl acetate. In certain embodiments, the composition comprises a polymer having pendant functional groups (such as halides, alcohols, or acyloxy groups) that can form ether bonds with hydroxyl groups on an ascaroside or ascaroside derivative, such as polyvinyl alcohol, polyvinyl chloride, or polyvinyl acetate. In certain embodiments, the composition comprises a polymer, such as a polyacrylic acid or polyacrylate, having pendant carboxyl or carboxyl ester groups that can esterify or transesterify with hydroxyl groups on an ascaroside or modified ascaroside or that can form anhydride linkages with carboxyl groups on an ascaroside.

[0240] In some embodiments, the structurally modified ascarosides as provided herein are oligomer-functionalized ascarosides or polymer-functionalized ascarosides, including ascarosides conjugated to naturally occurring oligomers, polymers, or biomolecules. In some embodiments, the structurally modified ascarosides include ascarosides covalently conjugated to starch, cellulose, lignin, or similar biopolymer materials.

[0241] In some embodiments of the polymer flanked by ascarosides, the flanked ascaroside molecules are attached to the polymer by non-covalent interactions (e.g., hydrogen bonds and / or ionic bonds). In some embodiments, the ascaroside molecules are covalently attached to the polymer directly or by various types of bonds, which are advantageously cleavable by environmental triggering, so that under certain conditions, the bonds are cleaved, releasing the ascaroside or its derivative. Examples of non-covalent bonds include mixtures of polycationic polymers or oligomers with carboxylate anions of ascarosides - for example, derived from ascarosides having carboxylic acid moieties on the side chains or derived from ascarosides that have been modified to provide such carboxylate groups (i.e., by reaction of ascaroside hydroxyl groups with cyclic anhydrides such as succinic anhydride, maleic anhydride, or phthalic anhydride). Examples of suitable covalent bonds include, but are not limited to, ether bonds, ester bonds, amide bonds, glycosidic bonds, urethane bonds, carbonate bonds, or siloxane bonds. Examples of particularly suitable covalent bonds include ester bonds, amide bonds, and glycosidic bonds.

[0242] In some embodiments, the rate of release of the ascaroside moiety from such structurally modified ascarosides can depend on the nature of the respective polymer properties, e.g., the hydrophilic / hydrophobic ratio, the linear / branched nature, the polymer length, the degree of cross-linking, the degree of non-covalent interactions (e.g., hydrogen bonding and / or ionic interactions), and the types of bonds within the structure. In some embodiments, the release properties depend at least in part on the nature of the bond connecting the ascaroside to the rest of the molecule; in some embodiments, the ascaroside can be released by hydrolysis, thermodynamic dissociation, microbial degradation, or another chemical reaction that breaks the bond connecting the ascaroside. The release properties can be effectively tuned by modifying these properties.

[0243] Physically modified ascarosides

[0244] In some embodiments, the release of the ascaroside is modified by physical methods, for example, by incorporating the ascaroside into a matrix designed for its modified release. In some such embodiments, the release of the ascaroside from the matrix can be based, for example, on diffusion and / or matrix degradation. It is worth noting that, although such embodiments are referred to herein as including "physical" modifications, such modifications do not exclude the presence of structural modifications, i.e., some of the methods provided below may result in changes in the ascaroside, resulting in the ascaroside structure being in fact modified to some extent (e.g., by introducing bonds (covalent or ionic) to one or more other components).

[0245] In certain embodiments, physically modified ascarosides are provided by mixing or compounding one or more ascarosides with a polymeric material ("organic compounding") and / or an inorganic material ("inorganic compounding"). In some embodiments, nanocomposites comprising ascarosides compounded with both polymeric and inorganic materials are provided.

[0246] In some embodiments, organically compounded ascarosides are provided. Organic compounding can involve mixing and / or blending of an organic component (e.g., a polymer resin) with one or more additives (here, one or more ascarosides and optionally one or more additional components, such as the agronomically acceptable excipients and additive types mentioned below). In some embodiments, such embodiments can be described as formulations in which the ascarosides are impregnated within the organic component. In some embodiments, compounding can involve heating (e.g., so that the organic component (e.g., polymer resin) is in molten form during mixing and / or blending). In some embodiments, compounding is performed during an extrusion process known in the art so that the resulting extrudate (which can be of different sizes and shapes) contains one or more ascarosides.

[0247] In some such embodiments, compounding includes forming a covalent bond between the organic (e.g., polymer) material and at least one of the one or more ascarosides. In other embodiments, substantially no covalent bond is formed between the organic (e.g., polymer) material and the ascarosides.

[0248] In certain embodiments, the ascaroside compositions compounded with the polymer include compositions obtained by reactive extrusion of a polymer with one or more ascarosides. For example, such compositions may include compositions obtained by reactive extrusion of a polyester, particularly a biodegradable polyester, with an ascaroside. Such reactive extrusion may partially or completely incorporate the ascaroside into the polymer structure, for example, by forming a covalent bond (e.g., by condensation or transesterification) with one or more carboxylic acid or hydroxyl groups present on the ascaroside.

[0249] The types of organic components that can be compounded with the ascarosides can vary widely. In some embodiments, the ascarosides are compounded with materials such as coconut husk fiber, peat, and / or pine bark. In some embodiments, the ascarosides are compounded with polymer resins; in these embodiments, generally any melt-processable polymer can be used to provide the organically compounded ascarosides. Certain such melt-processable polymers are biocompatible and / or biodegradable. Suitable polymers can include, but are not limited to, the types of polymers mentioned above, as well as, for example, polypropylene, polyethylene, poly(vinyl chloride), polystyrene, polyethylene terephthalate, polyethylene-vinyl acetate, polyurethane, acrylonitrile butadiene styrene (ABS), nylon, vegetable starch, cellulose, methylcellulose, cellulose acetate, polylactic acid (PLA), polyhydroxyalkanoates (PHA), and derivatives and copolymers of any two or more thereof.

[0250] In some embodiments, inorganically compounded ascarosides are provided. In this context, inorganic compounding can involve mixing and / or blending of an inorganic component with one or more additives (here, one or more ascarosides with optionally one or more additional components, such as the agronomically acceptable excipients and additive types mentioned below). In some embodiments, such embodiments can be described as formulations in which the ascarosides are impregnated, absorbed, or adsorbed into the inorganic component. Mixing can be performed in a variety of ways and can be performed at room temperature or elevated temperatures and may or may not include solvents or other adjuvants. The inorganic material can vary and in some embodiments may include one or more of perlite, vermiculite, sand, clay, talc, wood flour, peat, silica gel, mica, activated carbon, and the like. In some embodiments, the inorganic material can be a fertilizer, for example, ammonium phosphate, ammonium sulfate, urea, potassium chloride, superphosphate, herbicides such as sodium chlorate and sodium sulfate, insoluble siliceous materials such as sand, crushed walnut shells, clayey materials such as montmorillonite, kaolinite or other types of clay, diatomaceous earth, granulated corn cobs, soapstone, quartz, and agricultural minerals such as sulfur, gypsum, lime, calcium carbonate, etc., and any combination of two or more thereof.

[0251] In certain embodiments, the present invention provides formulated growth media containing any of the controlled-release ascaroside compositions described herein. Examples include formulated soilless mixes, such as those widely used in plant propagation and indoor gardening (e.g., mixtures containing defined materials such as peat moss, coconut fiber, vermiculite, perlite, etc.), and monocomponent media, such as perlite, vermiculite, and the like. Providing such growth media pre-fortified with a composition that releases ascarosides over time provides growers with a simple and economical way to treat plants with ascarosides, e.g., to protect such plants from pathogens. The ascaroside composition can be present in such growth media as particles specifically designed to release ascarosides, or can be incorporated into the medium as part of one of the typical components (e.g., in such a blend, the ascaroside composition can be compounded with perlite or vermiculite).

[0252] In some embodiments, more than one method as provided herein can be combined. For example, a structurally modified ascaroside as described above can be further physically modified by compounding the structurally modified ascaroside with an organic material or an inorganic material.

[0253] Methods of use and compositions

[0254] The modified ascarosides described herein can be used to treat living plants, seeds, soil surrounding plants, or soil in which seeds / seedlings are to be planted. In some embodiments, the modified ascarosides are applied to a portion of a plant, e.g., one or more of a root, stem, leaf, seed, and / or flower. Such methods can be performed at any one or more stages of the plant life cycle, e.g., from seed to seedling to growing plant to before or after harvest.

[0255] Although this is not the primary focus of the present invention, the inventors also recognize that the compositions and methods herein can be used to treat animals with ascarosides (including treating humans with ascarosides as therapeutic agents or nutraceuticals). Specifically, in certain embodiments, the present invention includes modified release formulations of ascr#7 (or derivatives or analogs thereof) for use in treating or ameliorating health conditions in animals and humans.

[0256] Advantageously, methods using the disclosed modified ascarosides allow for improved release of ascarosides (relative to methods using unmodified ascarosides), e.g., delayed release and / or controlled release and / or extended release. By "delayed release" is meant that upon application of the compound or composition to a plant or animal or its environment (e.g., soil), the ascarosides are not immediately available to the plant (or animal); rather, the ascarosides are released at some time after application (or upon certain environmental triggers, as referred to herein). By "controlled release" is meant that the ascarosides are released over time, e.g., at a substantially predetermined rate. By "extended release" is meant that the ascarosides are released over an extended period of time after application to a plant, animal, or soil that is longer than that achieved by application of the corresponding unmodified ascarosides. In some embodiments, the disclosed modified ascarosides release one or more ascarosides substantially only in response to an environmental trigger (e.g., conditions associated with changes in light, temperature, soil pH, humidity, enzymes, and the like). In some embodiments, the modified release provided by the modified ascarosides provided herein can allow for the use of less ascarosides in the same active period than direct application of an unmodified ascaroside composition. In some embodiments, such controlled release can reduce leaching of ascarosides, reduce evaporation of ascarosides, and reduce degradation (photolysis, hydrolysis, and / or microbial degradation) of ascarosides, any of which can remove or degrade ascarosides before they can perform their desired function.

[0257] In some embodiments, the disclosed treatment methods can protect growing plants in the manner described in U.S. Patent No. 10,136,595, which is incorporated herein by reference in its entirety. For example, such methods can enhance pathogen resistance and / or induce one or more plant defense responses (thereby inhibiting pathogen growth and / or infection) in (or near) plants to which the modified ascarosides are applied. The disclosed methods can enhance resistance to pathogens, including but not limited to oomycetes, bacteria, nematodes, viruses, and insects, such as but not limited to Pseudomonas syringae, Phytophthora infestans, Bleucophylla graminicola, Heterodera schachtii, Meloidogyne incognita, Meloidogyne hapla, and turnip crinkle virus. In some embodiments, such improved release characteristics allow the effective time of the modified ascarosides to be longer than the effective time of the corresponding treatment performed with (unmodified) ascarosides.

[0258] In some embodiments, the disclosed treatment methods can protect plants or plant-based products from contamination by pathogens, or prevent or delay the onset of plant spoilage, or function in a manner as described in patent applications PCT / US22 / 81895 and PCT / US23 / 17947 (each of which is incorporated herein by reference in its entirety).

[0259] The exact method of treating plants, seeds, or soil with the modified ascarosides is not particularly limited. Seeds, plants, and / or soil can be treated in accordance with the present disclosure, for example, by soaking, spraying, evaporation, atomization, broadcasting, smearing, side application, or in-furrow application. For example, in certain embodiments, plants or soil can be sprayed with a suitable liquid composition, a solid plastic mulch composition containing ascarosides as described above can be applied to the soil surrounding the plant, plants can be grown or propagated in a culture medium containing any of the modified compositions described herein (or in a pot or container formed from a composition as described herein), and / or a granular composition can be provided for in-furrow application or side application.

[0260] The plant type that can be processed according to the method disclosed in the present invention is not particularly limited, and can be, for example, fruit and vegetable plants, trees and shrubs. The non-limiting examples of the plant that can be processed according to the disclosed method include, but are not limited to, the plant selected from the group consisting of the following: tobacco, Arabidopsis, tomato, barley, potato, sweet potato, yam, cotton, soybean, strawberry, beet, corn, rice, wheat, rye, oat, sorghum, millet, bean, pea, apple, banana, pear, cherry, peach, plum, apricot, almond, grape, kiwi, mango, melon, papaya, walnut, hazelnut, pistachio, raspberry, blackberry, loganberry, blueberry, cranberry, orange, lemon, grapefruit, tangerine, lettuce, carrot, onion, broccoli, cabbage, avocado, cocoa, cassava, cotton and flax.

[0261] In the methods provided herein, the modified ascarosides can be applied directly to plants and / or soil, or can be formulated into compositions that can be applied to plants and / or soil. Thus, the present disclosure provides compositions that generally include at least one modified ascaroside (including, for example, structurally modified ascarosides and / or physically modified ascarosides) and one or more inert ingredients (e.g., one or more agronomically acceptable carriers). Preferably, the methods of the present invention use a non-toxic carrier.

[0262] The term "agronomically acceptable carrier" includes any carrier suitable for application to plants or soil, for example, conventional excipients in formulation technology, such as for forming solutions (e.g., directly sprayable or directly dilutable solutions), emulsions (e.g., emulsion concentrates and diluted emulsions), wettable powders, suspensions, soluble powders, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, polymer material encapsulation agents, coatable pastes, natural and synthetic materials impregnated with active compounds, and microcapsules in polymeric substances. These compositions can be produced in a known manner, for example, by mixing the modified ascaroside with one or more agronomically acceptable carriers, such as liquid solvents or solid carriers, optionally with additional components including, but not limited to, surfactants, including emulsifiers, dispersants, foam formers, colorants, processing aids, lubricants, fillers, reinforcing agents, flame retardants, light stabilizers, ultraviolet radiation absorbers, weathering stabilizers, plasticizers, release agents, fragrances, thermal insulation additives (e.g., silica), crosslinking agents, antioxidants, defoamers, buffers, pH adjusters, compatibilizers, drift control additives, extenders / stickers, tackifiers, plant penetrants, safeners, spreaders, and wetting agents, among others.

[0263] In some embodiments, at least one modified ascaroside is the sole active agent in the composition. In some embodiments, the composition comprises one or more additional ascarosides (e.g., in another modified form or in an unmodified form). In some embodiments, one or more other active agents (e.g., one or more pesticides, fertilizers, etc.) are included in the composition. The compositions containing modified ascarosides provided herein can be in a variety of forms, including solid and liquid forms.

[0264] If the agronomically acceptable carrier is water, in some embodiments, an organic solvent as an auxiliary liquid solvent may be added. Suitable liquid solvents include, for example, aromatic compounds (e.g., xylene, toluene, and alkylnaphthalene); chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons (e.g., chlorobenzene, vinyl chloride, and methylene chloride); aliphatic hydrocarbons (e.g., cyclohexane); paraffins (e.g., petroleum fractions, mineral oils, and vegetable oils); alcohols (e.g., butanol or ethylene glycol and their ethers and esters); ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone) and strong polar solvents (e.g., dimethylformamide and dimethyl sulfoxide).

[0265] Suitable agriculturally acceptable solid carriers include, for example, ammonium salts and ground natural minerals (e.g., kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth); ground synthetic minerals (e.g., highly dispersed silica, alumina and silicates); crushed and fractionated natural rocks (e.g., calcite, marble, pumice, sepiolite and dolomite); synthetic particles of inorganic and organic powders; particles of organic material (e.g., sawdust, coconut shells, corn cobs and tobacco stalks).

[0266] Suitable emulsifiers and foam formers include, for example, nonionic emulsifiers and anionic emulsifiers (eg, polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example, alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates and aryl sulfonates) protein hydrolysates.

[0267] Suitable dispersants include, for example, lignin sulfite waste liquors and methylcellulose. Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in powder, granular or lattice form, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids, such as cephalin and lecithin, and synthetic phospholipids, can be used in the disclosed compositions. Other additives can include, for example, mineral oils and vegetable oils.

[0268] Colorants such as inorganic pigments, for example, iron oxide, titanium oxide and Prussian blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as iron salts, manganese salts, boron salts, copper salts, cobalt salts, molybdenum salts and zinc salts may also be included in the composition.

[0269] Methods for preparing solid and liquid compositions for agrochemical applications are generally known and can be used in accordance with the present disclosure (where such methods involve adding one or more modified ascarosides to such compositions). As described above, in some embodiments, the compositions according to the present disclosure can be in the form of granular materials (including dusts, pellets, soluble powders, flowable powders, water-dispersible granules, etc.). In some embodiments, the compositions according to the present disclosure can be in liquid form (e.g., solutions, suspensions, or emulsions). The solubility of some modified ascarosides in water may be limited; therefore, in some embodiments, the ascarosides or modified ascarosides are dissolved in a water-miscible cosolvent (e.g., ethanol) to initially dissolve the modified ascarosides. Subsequently, in some embodiments, the dissolved modified ascarosides can be added to a suitable amount of water to provide an aqueous composition containing the modified ascarosides. In some embodiments, the composition is in the form of a granular material treated with a modified ascaroside-containing liquid. In some embodiments, the composition comprising the modified ascaroside is formed into a fiber or filament, and in some such embodiments, a woven or nonwoven textile (e.g., a film) can be produced from the fiber or filament. In some embodiments, the composition as provided herein is made into particles. In some embodiments, the composition as provided herein is in the form of a film, for example, a plastic mulch. In some embodiments, the composition as provided herein is in the form of a molded article, for example, a pot, container, bag, or sleeve in which a plant can be propagated or cultivated. Any of the solid compositions provided herein can be optionally coated by methods well known in the art to further delay the release of the modified ascaroside.

[0270] In some embodiments, methods are provided for producing compositions in which an ascaroside is compounded with a polymer (e.g., to form a film, fiber, pellet, molded or extruded article, or filament). Such compounding generally comprises heating or melting the polymer and blending the softened or molten polymer with the ascaroside. Such methods can produce a physical mixture of the ascaroside and the polymer, or can produce a copolymer (e.g., by a process such as reactive extrusion), wherein the ascaroside reacts with the polymer during the compounding process (e.g., by transesterification or condensation).

[0271] It is expected that the compounds, compositions and methods of the present application will encompass variations and modifications developed using the information of the embodiments described in this disclosure. The methods and processes described in this specification may be adapted or modified by one of ordinary skill in the relevant art.

[0272] It is understood that the use of titles in this disclosure is for the convenience of the reader. The presence and / or placement of titles is not intended to limit the scope of the subject matter described herein. Unless otherwise indicated, an embodiment located in a certain section of an application may be applied to other embodiments throughout the application, either alone or in combination.

[0273] Throughout the specification, when compositions, compounds or products are described as having, including or comprising specific components, or when processes and methods are described as having, including or comprising specific steps, it is also contemplated that there are articles, devices and systems of the present application that essentially consist of or consist of the components, and that there are processes and methods according to the present application that essentially consist of or consist of the processing steps.

[0274] It should be understood that the order of steps or the order in which certain actions are performed is not important as long as the method is still feasible. In addition, two or more steps or actions can be performed simultaneously.

[0275] All publications and patent applications mentioned in the specification are indicative of the levels of those skilled in the art to which the invention pertains. All publications and patent applications are incorporated herein by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.

[0276] Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims.

Claims

1. A structurally modified ascaroside selected from the group consisting of: a) an ascaroside-based oligomer or polymer comprising two or more ascaroside moieties, optionally comprising a linker moiety between adjacent ascaroside moieties; b) an oligomer- or polymer-functionalized ascaroside comprising an ascaroside moiety and one, two or three oligomers or polymers attached thereto; and c) an ascaroside-penned polymer comprising a polymer and one or more pendant ascaroside moieties attached thereto, optionally comprising a linker moiety between the polymer and the pendant ascaroside moieties.

2. The structurally modified ascaroside of claim 1, wherein the modified ascaroside is an ascaroside-based oligomer or polymer, and wherein the oligomer or polymer comprises two or more ascaroside moieties and has no linker moiety between adjacent ascaroside moieties.

3. The structurally modified ascaroside of claim 2, wherein adjacent ascaroside moieties are attached to each other via an ester bond formed by a hydroxyl group on a first ascaroside molecule and a carboxylic acid on a second ascaroside molecule.

4. The structurally modified ascaroside of claim 1, wherein the modified ascaroside is an ascaroside-based oligomer or polymer, and wherein the oligomer or polymer comprises two or more ascaroside moieties and has a linker moiety between adjacent ascaroside moieties.

5. The structurally modified ascaroside of claim 4, wherein the linker moiety is selected from the group consisting of ether, ester, amide, glycoside, urethane, carbonate, and siloxane moieties.

6. The structurally modified ascaroside of any one of claims 1 to 5, wherein the modified ascaroside is an ascaroside-based oligomer or polymer, wherein the oligomer or polymer comprises from two to one thousand ascaroside moieties.

7. The structurally modified ascaroside of claim 6, wherein the oligomer or polymer comprises from two to five hundred ascaroside moieties.

8. The structurally modified ascaroside of claim 6, wherein the oligomer or polymer comprises from two to one hundred ascaroside moieties.

9. The structurally modified ascaroside of claim 6, wherein the oligomer or polymer comprises two to ten ascaroside moieties.

10. The structurally modified ascaroside of claim 6, wherein the oligomer or polymer comprises at least ten ascaroside moieties.

11. The structurally modified ascaroside of claim 6, wherein the oligomer or polymer comprises at least twenty ascaroside moieties.

12. The structurally modified ascaroside of claim 6, wherein the oligomer or polymer comprises at least fifty ascaroside moieties.

13. The structurally modified ascaroside of claim 1, wherein the modified ascaroside is an oligomer or polymer functionalized ascaroside comprising an oligomer or polymer attached to the ascaroside.

14. The structurally modified ascaroside of claim 1, wherein the modified ascaroside is an oligomer or polymer functionalized ascaroside comprising two oligomers or polymers attached to the ascaroside.

15. The structurally modified ascaroside of claim 1, wherein the modified ascaroside is an oligomer or polymer functionalized ascaroside comprising three oligomers or polymers attached to the ascaroside.

16. The structurally modified ascaroside of any one of claims 13 to 15, wherein the oligomer or polymer comprises a biodegradable polymer.

17. The structurally modified ascaroside of any one of claims 13 to 15, wherein the oligomer or polymer is selected from the group consisting of chitosan, chitin, starch, lignin, agar, pectin, cellulose, other polysaccharides (e.g., bark, sawdust, other cellulosic wastes), poly(ethylene glycol), poly(caprolactone), poly(lactide), poly(glycolic acid), polybutene, poly(vinyl alcohol), poly(vinyl chloride), poly(citric acid), poly(acrylates), poly(aspartic acid), poly(ethylene), polyethylene vinyl acetate (PEVA), polystyrene, divinyl benzene, and derivatives and copolymers thereof.

18. The structurally modified ascaroside of claim 1, wherein the modified ascaroside is an ascaroside-pendent polymer comprising from about five to about five hundred ascaroside moieties attached thereto.

19. The structurally modified ascaroside of claim 1, wherein the modified ascaroside is a polymer with pendant ascarosides, and wherein the one or more pendant ascaroside moieties are directly bonded to the polymer.

20. The structurally modified ascaroside of claim 1, wherein the modified ascaroside is a polymer flanked with ascarosides comprising a linker moiety between the polymer and the one or more flanking ascaroside moieties.

21. The structurally modified ascaroside of claim 20, wherein the linker moiety is selected from the group consisting of ether, ester, amide, glycoside, urethane, carbonate, and siloxane moieties.

22. The structurally modified ascaroside of any one of claims 1 to 21, wherein the ascaroside moiety has structure (I) in: Z is an optionally substituted C 3-40 an aliphatic group, and R a and R b Each of which is independently -H, or an optionally substituted moiety selected from the group consisting of: C 1-20 Aliphatic group, C 1-20 Acyl, C 1-20 Heteroaliphatic, aryl, heteroaryl, hydroxyl protecting group, phosphorus-linked functional group, sulfur-linked functional group, silicon-linked functional group, C 2-20 Carbonate (e.g. part -C(O)OR c ), C 2-20 Carbamate (e.g., part -C(O)N(R c )2) C 2-20 Thioesters (e.g., moieties -C(S)R c ), C 2-20 Thiocarbonates (e.g., moieties -C(S)OR c ), C 2-20 Dithiocarbonates (e.g., part-C(S)SR c ), C 1-20 Thiocarbamates (e.g., moieties -C(S)N(R c ) 2), a sugar moiety, a peptide, a polymer chain, or a linker to another ascaroside molecule via a bond or a carbon-containing linker. c is independently selected at each occurrence from -H, optionally substituted C 1-12 aliphatic, optionally substituted C 1-12 heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, a polymer chain, or a linker to another ascaroside molecule via a bond or a carbon-containing linker, and wherein R a and R b Together they may form an optionally substituted ring, optionally containing one or more heteroatoms, and optionally containing one or more sites of unsaturation.

23. The structurally modified ascaroside of claim 22, wherein Z is selected from the group consisting of: (i) –CH(CH3)–R 1 , where R 1 is an optionally substituted C 1-40 aliphatic groups; (ii) –CH(CH3)–(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; (iii) –CH(CH3)–(CH2) n –CH=CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; (iv) –CH(CH3)–(CH2) n –CH(OH)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; (v) –CH(CH3)–(CH2) n –C(O)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; (vi)–(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; (vii)–(CH2) n –CH=CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; (viii)–(CH2) n –CH(OH)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; and (ix)–(CH2) n –C(O)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 heteroaliphatic groups, optionally substituted aromatic groups, optionally substituted heteroaryl groups, glycosides, amino acids, peptides, nucleotides, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety.

24. The structurally modified ascaroside of claim 22, wherein Z is selected from the group consisting of: (x)–CH(CH3)–(CH2) n –CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; (xi)–CH(CH3)–(CH2) n –CH=CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; (xii)–CH(CH3)–(CH2) n –CH(OH)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; (xiii) –CH(CH3)–(CH2) n –C(O)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; (xiv)–(CH2) n –CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; (xv)–(CH2) n –CH=CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; (xvi)–(CH2) n –CH(OH)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; or (xvii)–(CH2) n –C(O)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety.

25. The structurally modified ascaroside of any one of claims 22 to 24, wherein R a and R b Each is -H.

26. The structurally modified ascaroside of any one of claims 22 to 25, wherein Z is -CH(CH3)-(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide.

27. The structurally modified ascaroside of any one of claims 1 to 26, wherein at least one of the ascaroside moieties is ascr#18.

28. A physically modified ascaroside comprising one or more ascarosides compounded with an organic material or an inorganic material.

29. The physically modified ascaroside of claim 28, wherein the ascaroside is compounded with an organic material selected from the group consisting of coconut husk, peat and / or pine bark.

30. The physically modified ascaroside of claim 28, wherein the ascaroside is compounded with a polymer resin.

31. The physically modified ascaroside of claim 30, wherein the polymer resin is a biodegradable polymer.

32. The physically modified ascaroside of claim 30, wherein the polymer resin is a melt processable polymer.

33. The physically modified ascaroside of claim 30, wherein the polymer resin is selected from the group consisting of polypropylene, polyethylene, poly(vinyl chloride), polystyrene, polyethylene terephthalate, polyethylene-vinyl acetate, polyurethane, acrylonitrile butadiene styrene (ABS), nylon, vegetable starch, polylactic acid (PLA), polyhydroxyalkanoate (PHA), and derivatives and copolymers of any two or more thereof.

34. The physically modified ascaroside of claim 28, wherein the ascaroside is compounded with an inorganic material selected from the group consisting of perlite, vermiculite, sand, clay, talc, wood flour, peat, silica gel, mica, activated carbon, and combinations thereof.

35. The physically modified ascaroside of claim 28, wherein the ascaroside is compounded with an inorganic material selected from the group consisting of fertilizers (e.g., ammonium phosphate, ammonium sulfate, urea, potassium chloride, superphosphate), herbicides (e.g., sodium chlorate or sodium sulfate), insoluble siliceous materials (e.g., sand or crushed walnut shells), clayey materials (e.g., montmorillonite, kaolinite or other types of clay), diatomaceous earth, granulated corn cob, saponite, quartz, lead, iron, and agricultural minerals (e.g., sulfur, gypsum, lime, calcium carbonate, etc.), and combinations thereof.

36. The physically modified ascaroside of any one of claims 28 to 35, comprising one or more bonds between one or more of the ascarosides and the organic material or the inorganic material.

37. The physically modified ascaroside of any one of claims 28 to 35, further comprising one or more additional components selected from the group consisting of surfactants including emulsifiers, dispersants, foam formers, colorants, processing aids, lubricants, fillers, reinforcing agents, flame retardants, light stabilizers, ultraviolet radiation absorbers, weathering stabilizers, plasticizers, release agents, fragrances, thermal insulation additives (e.g., silica), crosslinking agents, antioxidants, defoamers, buffers, pH adjusters, compatibilizers, drift control additives, extenders / stickers, tackifiers, plant penetrants, safeners, spreaders, and wetting agents.

38. The physically modified ascaroside of any one of claims 28 to 37, wherein at least one of the ascaroside has structure (I) in: Z is an optionally substituted C 3-40 an aliphatic group, and R a and R b Each of which is independently -H, or an optionally substituted moiety selected from the group consisting of: C 1-20 Aliphatic group, C 1-20 Acyl, C 1-20 Heteroaliphatic, aryl, heteroaryl, hydroxyl protecting group, phosphorus-linked functional group, sulfur-linked functional group, silicon-linked functional group, C 2-20 Carbonate (e.g. part -C(O)OR c ), C 2-20 Carbamate (e.g., part -C(O)N(R c )2) C 2-20 Thioesters (e.g., moieties -C(S)R c ), C 2-20 Thiocarbonates (e.g., moieties -C(S)OR c ), C 2-20 Dithiocarbonates (e.g., part-C(S)SR c ), C 1-20 Thiocarbamates (e.g., moieties -C(S)N(R c ) 2), a sugar moiety, a peptide, a polymer chain, or a linker to another ascaroside molecule via a bond or a carbon-containing linker. c is independently selected at each occurrence from -H, optionally substituted C 1-12 aliphatic, optionally substituted C 1-12 heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, a polymer chain, or a linker to another ascaroside molecule via a bond or a carbon-containing linker, and wherein R a and R b Together they may form an optionally substituted ring, optionally containing one or more heteroatoms, and optionally containing one or more sites of unsaturation.

39. The physically modified ascaroside of claim 38, wherein Z is selected from the group consisting of: i.–CH(CH3)–R 1 , where R 1 is an optionally substituted C 1-40 aliphatic groups; ii.–CH(CH3)–(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; iii.–CH(CH3)–(CH2) n –CH=CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; iv.–CH(CH3)–(CH2) n –CH(OH)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; v.–CH(CH3)–(CH2) n –C(O)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; vi.–(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; vii.–(CH2) n –CH=CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; viii.–(CH2) n –CH(OH)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a glycoside, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; and ix.–(CH2) n –C(O)–CH-CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 heteroaliphatic groups, optionally substituted aromatic groups, optionally substituted heteroaryl groups, glycosides, amino acids, peptides, nucleotides, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety.

40. The physically modified ascaroside of claim 38, wherein Z is selected from the group consisting of: x.–CH(CH3)–(CH2) n –CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; xi.–CH(CH3)–(CH2) n –CH=CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; xii.–CH(CH3)–(CH2) n –CH(OH)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; xiii.–CH(CH3)–(CH2) n –C(O)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; xiv.–(CH2) n –CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; xv.–(CH2) n –CH=CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; xvi.–(CH2) n –CH(OH)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety; or xvii.–(CH2) n –C(O)–CH-CON(R 3 )2, wherein n is an integer from 1 to 40, and each R 3 are independently -H, optionally substituted C 1-20 An aliphatic group, an optionally substituted C 1-20 a heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaryl group, a polymer chain, an amino acid, a peptide, a nucleotide, or linkage to another ascaroside molecule via a bond or a carbon-containing linker moiety.

41. The structurally modified ascaroside of claim 38, wherein R a and R b Each is -H.

42. The structurally modified ascaroside of any one of claims 38 to 41, wherein Z is -CH(CH3)-(CH2) n –CO2R 2 , wherein n is an integer from 1 to 40, and R 2 is -H, a metal cation, an optionally substituted C 1-20 an aliphatic group, an optionally substituted aromatic group, a glycoside, an amino acid, a peptide or a nucleotide.

43. The physically modified ascaroside of any one of claims 28 to 42, wherein at least one of the ascaroside moieties is ascr#18.

44. A composition comprising the structurally modified ascaroside of any one of claims 1 to 27 and / or the physically modified ascaroside of any one of claims 28 to 42 and one or more agronomically acceptable excipients or additives.

45. The composition of claim 44 in liquid form.

46. ​​The composition of claim 45, wherein the liquid is a sprayable formulation.

47. The composition of claim 44 in solid form.

48. The composition of claim 47, wherein the solid comprises particles.

49. The composition of claim 47, wherein the solid comprises a plastic covering.

50. The composition of claim 47, wherein the solid composition is a film.

51. A method comprising: contacting a plant or part thereof, or soil surrounding the plant or part thereof, with a structurally modified ascaroside according to any one of claims 1 to 27, a physically modified ascaroside according to any one of claims 28 to 43, or a composition according to any one of claims 42 to 48, The ascaroside or composition is effective in improving the resistance of a plant to one or more pathogens and / or inducing an immune response in the plant or a part thereof.

52. The method of claim 51, wherein the part thereof is selected from the group consisting of roots, stems, leaves, seeds and flowers.

53. A method as claimed in claim 51 or claim 52, wherein the plant is a vegetable or fruit plant.

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