US 2010O2551 24A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0255124 A1 Green et al. (43) Pub. Date: Oct. 7, 2010

(54) COMPOSITIONS OF VOLATLE ORGANIC Publication Classification COMPOUNDS AND METHODS OF USE THEREOF (51) Int. Cl. AOIN 65/00 (2009.01) (75) Inventors: Wayne A. Green, Encinitas, CA AOIN 37/02 (2006.01) (US); Gary A. Strobel, Bozeman, AOIP3/00 (2006.01) MT (US) AOIP5/00 (2006.01) AOIP 7/00 (2006.01) Correspondence Address: AOIP I/00 (2006.01) Synthetic Genomics, Inc. CI2O 1/02 (2006.01) c/o DLA Piper LLP (US) CI2N I/00 (2006.01) 43.65 Executive Drive, Suite 1100 San Diego, CA 92.121-2133 (US) (52) U.S. Cl...... 424/725; 514/546; 435/29: 435/243 (73) Assignee: Synthetic Genomics, Inc., La Jolla, (57) ABSTRACT CA (US) The present invention provides compositions and methods for (21) Appl. No.: 12/753,714 treating, inhibiting or preventing the developing of a plant pathogenic disease. The compositions comprise volatile (22) Filed: Apr. 2, 2010 organic compounds effective to inhibit the growth of, or kill pathogenic microbes, including Ganoderma bominense. Related U.S. Application Data Invention compositions are especially useful in preventing (60) Provisional application No. 61/166.694, filed on Apr. and treating basal stem rot in the oil palm, and can be applied 3, 2009, provisional application No. 61/230,672, filed in the vicinity of the plant or used to sterilize the plant growth on Jul. 31, 2009. medium prior to or concurrent with plant growth therein.

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COMPOSITIONS OF VOLATLE ORGANIC palms are immediately exposed to a high load of inoculum COMPOUNDS AND METHODS OF USE (spores) and eventually become infected by Ganoderma bon THEREOF inense. 0007. It is widely believed that the problem of basal stem CROSS REFERENCES TO RELATED rot of palm will become increasingly serious as more and APPLICATIONS more established plantations become due for second or even third replanting. Environmental considerations, coupled with 0001. This application claims priority under 35 U.S.C. governmental directives, will reduce exploitation of new for S119(e) to U.S. Patent Application NO. 61/166,694 filed on est areas, making further replanting of these crops necessary. Apr. 3, 2009 add U.S. Patent Application No. 61/230,672 filed There is a need for integrated management systems for Gano on Jul. 31, 2009, the entire contents of which are hereby derma and related diseases to maintain the Success of the oil incorporated by reference. palm industry.

FIELD OF THE INVENTION SUMMARY OF THE INVENTION 0002 The present invention relates to compositions of 0008. The compositions of the present invention may be Volatile organic compounds with biological activity against used to control major diseases of plants caused by a variety of plant pathogens, particularly the fungus Ganoderma bonin plant pathogens. One exemplary plant is the oil palm, ense that is a causative agent of the oil palm disease Gano whereby compounds may inhibit or prevent the development derma Basal Stem Rot. The disclosure also provides compo of basal stem rot disease. These compounds may target Gano sitions comprising at least one known pesticidal agent useful derma bominense, a causative agent of basal stem rot disease. for selective pest control applications. 0009. One aspect of the invention provides a composition for treating, inhibiting or preventing at least one plant patho BACKGROUND OF THE INVENTION genic disease. The composition comprises two or more com pounds wherein at least one of the compounds is isobutyric 0003. Oil palm, Elaeis guineensis, is the most important acid, methyl isobutyrate or isobutyric anhydride. The second plantation crop in Malaysia. Four tons of palm oil are pro compound of the composition is selected from isobutyric duced annually per hectare from this crop plant. Many Small acid, methyl isobutyrate, isobutyric anhydride, ethyl isobu private landowners are able to profit from the production and tyrate, propyl isobutyrate, isobutyric acid-allyl ester, naph sale of the palm oil, making this an activity of great economic thalene, caryophyllene, and a plant essential oil. The compo importance. Presently, Malaysia's oil palm industry is under sition may also be a combination of three or more or these threat as it is faced with a very serious plant disease problem. compounds, or may further include additional components, This problem is a prevailing incurable oil palm disease called including Volatile organic compounds (VOCs). Additional Ganoderma Basal. Stem Rot (BSR) caused by Ganoderma compounds may include, but are not limited to, one or more of bominense. Presently, BSR is rapidly becoming the major naphthalene or naphthalene derivatives, caryophyllene, iso threat to oil palm cultivation and palm oil production in caryophyllene, C-humulene, and the compounds provided in Southeast. Asia. Table 1 herein; compounds produced by Muscodor species, 0004. In BSR disease, basal stem rot is only one part of the Such as the Volatile organic compounds listed in Table 2 disease cycle. Ganoderma bominense also causes a seedling herein; and plant essential oils, such as those listed in Table 3 disease and an upper stem rot of more developed palms. herein. Spores of G. bominense have multiple roles in the infection 0010. In some preferred embodiments, the composition process to bring about the three distinct phases of this impor includes 20-70% isobutyric acid, 20-70% methyl isobutyrate, tant plant disease. This pathogenic organism is also prevalent 20-70% isobutyric anhydride, or any combination thereof. In on other major plantation plants including coconut, betel nut, further embodiments, this composition further comprises tea, cacao, acacia and poplar. 1-10% naphthalene, caryophyllene, or a plant essential oil. In 0005. With no effective cure at present, BSR has a huge certain preferred embodiments, the composition comprises economic impact on the Malaysian oil palm industry. Thus, 42-53% isobutyric acid, 42-53% methyl isobutyrate, and plant health is crucial in obtaining maximal productivity of 3-7% naphthalene, caryophylene, or a plant essential oil. In the oil palm and techniques, methods and management ideas other preferred embodiments, the composition includes are needed to control BSR. Attempts to control this disease 42-53% isobutyric acid, 42-53% isobutyric anhydride, and with agrochemicals have not been very Successful. This could 3-7% naphthalene, caryophyllene, or a plant essential oil. be due to the fact that the oil palms already possessed latent 0011. In other preferred embodiments, the composition fungal infections at the time of the chemical treatment. Bio further comprises an agriculturally effective amount of a pes logical control agents have also been tried against Gano ticidal compound or composition. The additional compound derma with limited Success. Saprophytic organisms (such as or composition may be an acaricide, a bactericide, a fungi Trichoderma harzianum) merely arrest the spread of disease cide, an insecticide, a microbicide, a nematicide, or a food by competing against Ganoderma to reduce its opportunity to preservative. colonize oil palm roots. 0012. The composition in some embodiments may be in 0006 BSR is a particular concern because the activity of the form of a powder, a granule, a pellet, a gel, an aqueous replanting oil palms can accelerate spread of the disease. It is Suspension, a solution or an emulsion. The composition may well known that successive replanting of oil palms can be be provided with a carrier, such as an agriculturally accept rapidly exploited by soil borne fungi such as Ganoderma. able carrier. The carrier can be a seed. Soils that continuously support the growth of palms eventu 0013 Another aspect of the invention provides a method ally act as a reservoir for Ganoderma fruiting structures and for treating, inhibiting or preventing the development of a spores of this organism. Soils that are replanted with new plant pathogenic disease, comprising applying a composition US 2010/02551 24 A1 Oct. 7, 2010 of the invention in the vicinity of the plant. In a preferred stood and commonly employed using conventional method embodiment, the pathogen may be Aspergillus fumigatus, ology by those skilled in the art. Botrytis cinerea, Cerpospora betae, Curvularia sp., Gano 0020. The singular form an’, and “the' include plu derma bominense, Geotrichum candidum, Mycosphaerella ral references unless the context clearly dictates otherwise. fijiensis, Phytophthora palmivora, Phytophthora ramorum, For example, the term “a cell includes one or more cells, Pythium ultimum, Rhizoctonia Solani, Rhizopus sp., Schizo including mixtures thereof. phyllum sp., Sckrotinia Sclerotiorum, Verticillium dahliae, or 0021 Bactericidal: The term “bactericidal', as used Xanthomonas axonopodis. In another preferred embodiment, herein, refers to the ability of a substance to increase mortality the host plant is Susceptible to disease caused by Ganoderma or inhibit the growth rate of bacteria. bominense. In another preferred embodiment, the host plant is 0022 Biological control: As used herein, “biological con an oil palm plant. In certain embodiments, the method is trol' is defined as control of a pathogen or insector any other effective to inhibit the growth of the plant pathogen. In pre undesirable organism by the use of a second organism. An ferred embodiments, the method is effective to kill the plant example of a known mechanism of biological control is the pathogen use of enteric bacteria that control root rot by out-competing 0014 Some embodiments provide for the composition to fungi for space on the Surface of the root. Bacterial toxins, be applied to the vicinity or a plant. Such as around the roots, Such as antibiotics, have been used to control pathogens. The stems, trunk, seed, or leaves of the plant, applied onto Such toxin can be isolated and applied directly to the plant or the parts of the plant, or injected into Such parts of the plant. In bacterial species may be administered so it produces the toxin other embodiments, the composition can be used to treat or in situ. sterilize the soil or plant growth medium, by exposing the soil 0023 Culturing: The term “culturing, as used herein, or plant growth medium to vapors from the invention com refers to the propagation of organisms on or in media of position, or by direct contact, such as intermixing, with the various kinds. composition. 0024 Composition: A “composition' is intended to mean 0015. Another aspect of the invention provides a method a combination of active agent and another compound, carrier for Screening microbial strains that may be useful for treating, or composition, inert (for example, a detectable agent or label inhibiting or preventing the development of a plant patho or liquid carrier) or active, Such as a pesticide. genic disease. The method comprises (i) exposing or contact 0025 Derivative: As used herein, a “derivative' of a ing candidate microbial Strains with an invention composi chemical compound is a compound that can be chemically or tion, (ii) selecting microbial strains resistant to the biologically derived from the original compound, for composition, and (iii) characterizing the selected microbial example by the addition, substitution or deletion of chemical strain. The invention also includes the microbial strains components of the original compound. For example, a deriva obtained from the method as described above. tive may be an isomer of the referenced compound, an anhy 0016. Another aspect of the invention relates to a method dride of the referenced compound, or has one or more chemi for killing, inhibiting or preventing the development of an cal groups added or substituted with respect to the referenced undesired organism, such as a fungus, a bacterium, a micro compound. For example, propanoic acid, 2-methyl 3-meth organism, a nematode, and an insect. The method comprises ylbutyl ester is considered to be a derivative of propanoic exposing or contacting the organism to or with an effective acid. amount of an invention composition. 0026. Effective amount: An "effective amount’, as used 0017. These and other objects and features of the invention herein, is an amount sufficient to affect beneficial or desired will become more fully apparent when the following detailed results. An effective amount can, be administered in one or description of the invention is read in conjunction with the more administrations. In terms of treatment, inhibition or accompanying drawing. protection, an effective amount is that amount Sufficient to ameliorate, stabilize, reverse, slow or delay progression of the BRIEF DESCRIPTION OF THE DRAWINGS target infection or disease states. 0027 Fungicidal: As used herein, “fungicidal refers to 0018 FIG. 1 depicts the effect of treating soil with a com the ability of a substance to decrease the rate of growth of position of the invention. Treated soil on the right shows no fungi or to increase the mortality of fungi. growth of microorganisms on soil inoculated with Gano 0028 Fungus: The term “fungus' or “fungi', as used derma bominense; while the untreated control plate on the left herein, includes a wide variety of nucleated spore-bearing shows extensive growth. organisms that are devoid of chlorophyll. Examples of fungi include yeasts, molds, mildews, rusts, and mushrooms. DETAILED DESCRIPTION OF THE INVENTION 0029. Insecticidal: As used herein, Insecticidal refers to Definitions the ability of a substance to increase mortality or inhibit the growth rate of insects or their larvae. 0019. Unless otherwise defined, all terms of art, notations 0030 Microbicidal: “Microbicidal, as used herein; refers and other Scientific terms or terminology used herein are to the ability of a substance to increase mortality or inhibit the intended to have the meanings commonly understood by growth rate of microorganism. those of skill in the art to which this invention pertains. In 0031. Mutant: As used herein, the term “mutant” or “vari Some cases, terms with commonly understood meanings are ant” refers to a modification of the parental strain in which the defined herein for clarity and/or for ready reference, and the desired biological activity remains similar to that of the inclusion of such definitions herein should not necessarily be parental Strain. Mutants or variants may occur in nature with construed to represent a substantial difference over what is out the intervention of man. They also are obtainable by generally understood in the art. Many of the techniques and treatment with or by a variety of methods and compositions procedures described or referenced herein are well under known to those of skill in the art. For example, parental strains US 2010/02551 24 A1 Oct. 7, 2010 may be treated with a chemical such as N-methyl-N'-nitro organism for effectiveness. The invention compositions are N-nitrosoguanidine, ethylmethanesulfone, or by irradiation thus placed in the vicinity of the host plant or the target using gamma, X-ray, or UV-irradiation, or by other means organism, or in the growth medium or soil of the host plant well known to those practiced in the art. prior to or concurrent with plant growth. Generally, volatile 0032 Nematicidal: The term “nematicidal', as used compounds are in the vicinity of the target pathogenic organ herein, refers to the ability of a substance to increase mortality ism so long as they achieve their biological effect prior to or inhibit the growth rate of nematodes. evaporation. They may be spread on or around the base of the 0033 Plant oil: A “plant oil”, “plant essential oil”, or host plant or intermixed with the growth medium or soil of the “plant volatile oil, as used herein, is any oil derived from any plant. Physical contact with the host plant or target pathogen part of a plant, and includes any compound purified or derived is not required due to the dispersal of the volatiles through the from a plant oil. Such as a hydrophobic, Volatile organic air or soil. compound that is produced by a plant species. An exemplary 0036. The discussion of the general methods given herein plant essential oil is caryophyllene, a natural bicyclic sesquit is intended for illustrative purposes only. Other alternative erpene that is a constituent of many plant essential oils, such methods and embodiments will be apparent to those of skill in as oils obtained from cannabis (Cannabis sativa), hemp, the art upon review of this disclosure. Marijuana, caraway (Carum carvi), cloves (Syzygium aromi aticum), hops (Humulus lupulus), basil (Ocimum), oregano Compositions of Volatile Organic Compounds (Origanum vulgare), pepper (Piper nigrum), rosemary (Ros marinus oficinalis), cinnamon (Cinnamomum zeylanicum or 0037. The invention provides compositions of volatile tamala). A plant essential oil used in a composition as dis organic compounds that can be used to treat or prevent growth closed herein need not be isolated from a plant, for example, of a pathogen, Such as but not limited to a plant pathogen. it may be chemically synthesized or isolated from a microor Table 1 provides exemplary compounds that can be used in ganism that produces the compound. Exemplary plant essen compositions and methods of the present invention. Table 2 tial oils are provided in Table 3 herein. herein provides the VOCs produced by a fourteen day old 0034 Pesticidal: The term "pesticidal, as used herein, culture of Muscodor strobelii. M. Strobelii producing these refers to the ability of a substance to decrease the rate of compounds was demonstrated to be lethal to several species growth of a pest, i.e., an undersired organism, or to increase of pathogenic microorganisms including Aspergillus filmiga the mortality of a pest. tus, Botrytis cinerea, Cerpospora betae, Curvularia sp., 0035 Volatile. “Volatile compounds” and “volatile Ganoderma bominense, Geotrichum candidum, Mycosphaer organic compounds” (VOCs), as used herein, are compounds ella fifiensis, Phytophthora palmivora, Phytophthora that in most instances evaporate readily at ambient tempera ramorum, Pythium ultimum, Rhizoctonia Solani, Rhizopus ture and pressure. Volatile compounds of the present inven sp., Schizophyllum sp., Sclerotinia Sclerotiorum, Verticillium tion must be present “in the vicinity” of the target pathogenic dahliae, and Xanthomonas axonopodis.

TABLE 1 Compounds of the present invention. Compound IUPAC name CAS Registry # MW ethanol ethanol 64-17-5 46 80COile propanone 67-64-1 58 2-butanone butan-2-one 78-93-3 72 methyl acetate methyl acetate 79-20-9 74 isobutyl alcohol 2-methylpropan-1-ol 78-83-1 74 isobutyric acid 2-methylpropanoic acid 79-31-2 88 ethyl acetate ethyl acetate 141-78-6 88 N,2-dimethylpropanamide 2675-88-9 O1 isobutyric acid, methyl ester methyl-2-methylpropanoate S47-63-7 O2 (methyl isobutyrate) 1-(ethenyloxy)-3-methyl-butane 39782-38-2 14 Octane Octane 111-65-9 14 methyl 2-methoxypropenoate 17639-76-8 16 butyl acetate butyl ethanoate 123-86-4 16 isobutyl acetate isobutyl acetate 110-19-0 16 isobutyric acid, ethyl ester ethyl-2-methylpropanoate 97-62-1 16 (ethyl isobutyrate) phenethyl alcohol 2-phenylethanol 60-12-8 22 allyl 2-methylpropanoate 15727-77-2 28 naphthalene naphthalene 91-20-3 28 methyl 2,3-dimethylbutanoate 3OS4O-29-5 30 isobutyric acid, propyl ester propyl-2 methylpropanoate 644-49-5 30 (propyl isobutyrate) 3-methyl-1-butanol 3-methyl-1-butanol 123-51-3 31 2-nonanone heptyl methyl ketone 821-55-6 42 2-methylheptanoic acid 1188-O2-9 44 acetic acid, (tert-butylthio)- 2431O-22-3 48 pentamethyl-benzene 700-12-9 48 2-(1-Propenyl)-6-methylphenol 48 US 2010/02551 24 A1 Oct. 7, 2010

TABLE 1-continued Compounds of the present invention. Compound IUPAC name CAS Registry # MW undecane undecane 1120-21-4 1S6 isobutyric anhydride 2-methylpropandyl 2-methylpropanoate 97-72-3 158 44-diethyl-2,5-octadiyne 61227-87-O 162 butyl propyl oxalate 264.04-30-8 188 4,5-dimethyl-1,2,3,6,7,8,8a,8b 188 octahydrobiphenylene 45-dehydro-isolongifolene 2O2 alpha-gurunene 489-40-7 204 (-)-arstolene 25274-27-5 204 alpha-patchoulene S60-32-7 204 (-)-tricyclo6.2.1.0(4.11) undec-5- 204 ene, 1.5.9.9-tetramethyl (isocaryophyllene-II) bergamotene 6895-56-3 204 (Z)-7,11-dimethyl-3-methylene 204 1,6,10-dodecatriene caryophyllene 4,11,11-trimethyl-8-methylene 87-44-5 204 bicyclo7.2.0]undec-4-ene heptyl allyl oxalate 228 isoamyl isobutyrate 3-methylbutyl 2-methylpropanoate 2OSO-01-3 316

0038. In some embodiments of the invention, a composi Additional compounds may include, but are not limited to, tion used to inhibit or prevent development of a plant patho one or more of naphthalene ornaphthalene derivatives, caryo genic disease, or infestation by a plant pathogen comprises at phyllene, isocaryophyllene, C-humulene, and the compounds least 20 percent, at least 25 percent, at least 30 percent, at least provided in Table 1 herein; compounds produced by Mus 35 percent, at least 40 percent, at least 45 percent, at least 50 codor species, such as the Volatile organic compounds listed percent, at least 55 percent, at least 60 percent, at least 65 in Table 2 herein; and plant essential oils, such as those listed percent or at least 70 percent isobutyric acid, methyl isobu in Table 3, herein. tyrate or isobutyric anhydride. A preferred range is 20-70%, 0042. For example, Muscodor albus produces, among other VOCs, octane, acetone, ethanol, isobutyl alcohol, 30-60%, or 40-50%, and a most preferred range is 42-53%. methyl acetate, ethyl acetate, various methyl esters of pro 0039. In some embodiments, a composition of the inven panoic acid, butanol derivatives, furan, nonanone derivatives, tion further includes, as a second compound, at least 20 per naphthalene, aZulene, cyclohexene and caryophyllene (U.S. cent, at least 25 percent, at least 30 percent, at least 35 percent, Pat. No. 6,911.338, incorporated herein by reference). Mus at least 40 percent, at least 45 percent, at least 50 percent, at codor vitigenus produces, for example, naphthalene and least 55 percent, at least 60 percent, at least 65 percent, or at naphthalene derivatives, among other VOCs (U.S. Pat. No. least 70 percent isobutyric acid, methyl isobutyrate, isobu 7.267,975, incorporated herein by reference). VOCs identi tyric anhydride, ethyl isobutyrate, propyl isobutyrate, isobu fied as produced by M. Strobelii are provided herein in Table tyric acid-allyl ester. A preferred range is 20-70%, 30-60%, or 2. Volatile compounds produced by M. albus, M. vitigenus, or 40-50%, and a most preferred range is 42-53%. M. Strobelii can be used in a composition of the invention, in 0040. In some embodiments, a composition of the inven addition to derivatives of these compounds. tion further includes, as a second or third compound, at least 0043. Other compounds that can be included, in a compo 1 percent, at least 2 percent, at least 3 percent, at least 4 sition of the invention include plantessential oils. Plantessen percent, at least 5 percent, at least 6 percent, at least 7 percent, tial oils can include Volatile hydrocarbon compounds at least 8 percent, at least 9 percent or at least 10 percent of obtained from any part of a plant, including the leaves, stems, naphthalene, caryophyllene or a plant essential oil. A pre roots, seeds, bark, wood, fruit (including rinds), or flowers of ferred range is 1-10%, 2-9%, or 3-8%, and a most preferred plant, or any oil derived from any plant parts. Included with range is 3-7%. out limitation are oils extracted or derived from Mentha 0041. A composition of the invention can include one or arvensis, Eucalyptus, Lisea cubea, peppermint, spearmint, more additional compounds, which can be any compounds wintergreen, clove, lemon, grapefruit, lime, tangerine, and that do not negatively affect the ability of the composition to orange, as well as oils extracted or derived from allspice or inhibit the growth of or kill one or more pathogenic microor juniper berries, from anise, celery; or cumin seeds, or from ganisms, where a pathogenic microorganism can be a micro almonds or nutmeg, and any constituents or derivatives organism that causes disease in a plant or an animal. In some thereof. Also included are oils extracted orderived from basil, examples, a composition of the invention includes one or bay, cinnamon, usage, lemon grass, Melaleuca, oregano, more VOCs in addition to isobutyric acid, methyl isobutyrate, rosemary, patchouli, pine, cannabis, chamomile, Sage, clove, or isobutyric anhydride. For example, the composition can geranium, hops, hyssop, jasmine, lavender, manuka, marjo include additional VOCs produced by M. Strobelii or other ram, camphor, rosewood, cedarwood, Sandalwood, agar fungi, including other Muscodor species. A composition may Wood, ginger, galangal, tea tree, bergamot, and Valerian, and also be a combination of three or more orthese compounds, or any constituents orderivatives thereof. Table 3 provides some may further include additional components, including Vola examples of plant essential oils that can be used in composi tile organic compounds (VOCs) and plant essential oils. tions of the invention. US 2010/02551 24 A1 Oct. 7, 2010

0044 An exemplary composition of the invention is a phyllene-II), bergamotene orderivatives thereof, patchoulene mixture of isobutyric acid, methyl isobutyrate, and naphtha or derivatives thereof (e.g., alpha-patchoulene), gurunene or lene. For example, compositions may comprise 20-70% derivatives thereof (e.g., alpha-gurunene), aristolene or isobutyric acid, 20-70% methyl isobutyrate, and 1-10% naph derivatives thereof (e.g., (-)-aristolene, or isolongifolene or thalene. In some embodiments, the composition comprises derivatives thereof (e.g., 4.5-dehydro-isolongifolene) present 30-60% isobutyric acid. In some embodiments, the compo individually at molar percentages of 10 percent or less in the sition comprises 30-60% methyl isobutyrate. In some mixture of VOCs produced by a Muscodor strain can be embodiments, the composition comprises 42-53% isobutyric present in a composition of the invention. acid, 42-53% methyl isobutyrate, and 34% naphthalene. For 0050. The disclosure provides compositions of com example, the composition can comprises 47.5% isobutyric pounds and optionally a carrier. The carrier may be any one or acid, 47.5% methyl isobutyrate, and 5% naphthalene. more of a number of carriers that confer a variety of proper 0045 Another exemplary composition is a mixture of ties, such as increased stability, wettability; dispersability, isobutyric acid, isobutyric anhydride, and naphthalene. For etc. Suitable formulations that may be prepared include wet example, compositions may comprise 20-70% isobutyric table powders, granules, pellets, gels, microencapsulated par acid, 20-70% isobutyric anhydride, and 1-10% naphthalene. ticles, and the like, liquids such as aqueous flowables, aque In some embodiments, the composition comprises 30-60% ous Suspensions, etc. The carrier may be an agricultural isobutyric acid. In some embodiments, the composition com carrier. In certain embodiments the carrier is a seed, and the prises 30-60% isobutyric anhydride. In some embodiments, composition may be applied or coated onto the seed or the composition comprises 42-53% isobutyric acid, 42-53% allowed to saturate the seed. isobutyric anhydride, and 3-7% naphthalene. For example, 0051. The agricultural carrier may be soil or plant growth the composition can comprise 47.5% isobutyric acid, 47.5% medium. Other agricultural carriers that may be used include isobutyric anhydride, and 5% naphthalene. water, fertilizers, plant-based oils, humectants, or combina 0046. Other examples of compositions of the invention tions thereof. The composition can be provided as a solution include mixtures of isobutyric acid, an isobutyric acid deriva that is injected or intermixed into the soil. The composition tive, and one or more plant essential oil, which can be any can be formulated as a particle or granule having a coating plant essential oil, including but not limited to plant essential that dissolves over time or on wetting to release the volatile oils as provided in Table 3. In some embodiments, a plant composition. essential oil used in a composition of the invention is caryo 0.052 Alternatively, the agricultural carrier may be a solid, phyllene or a derivative of caryophyllene, such as isocaryo Such as diatomaceous earth, alginate, clay, other plant and phyllene or C-humulene. For example, in Some embodiments, animal products, or combinations, including granules or Sus a composition includes 20-70% isobutyric acid, 20-70% pensions. For example, the aqueous Suspension, Solution, or methyl isobutyrate or isobutyric anhydride, and 1.10% of a emulsion may be provided with a carrier to facilitate dispersal plant essential oil. of the composition through the soil. Materials such as ver 0047 One exemplary composition is a mixture of isobu miculite, peat, natural or man-made fibers, or biological tyric acid, methyl isobutyrate, and caryophyllene. For material such as seed, plant parts, empty fruit bunches (EFBs) example, compositions may comprise 20-70% isobutyric from palm, Sugar cane bagasse, hulls or stalks from grain acid, 20-70% methyl isobutyrate, and 1-10% caryophyllene. processing, ground plant material (yard waste’) or wood In some embodiments, the composition comprises 30-60% from building site refuse, sawdust or small fibers from recy isobutyric acid. In some embodiments, the composition com cling of paper, fabric, or wood can be soaked in the compo prises 30-60% methyl isobutyrate. In some embodiments, the sition, and then mixed with the soil or growth medium used composition comprises 42-53% isohutyric acid, 42-53% for planting a plant species of interest. The agricultural car methyl isobutyrate, and 3-7% caryophyllene. For example, rier, Soil or plant growth medium need not be in direct contact the composition can comprises 47.5% isobutyric acid, 47.5% with the composition, for example, it can be treated or steril methyl isobutyrate, and 5% caryophyllene. ized by, vapors from the composition in the vicinity. 0048. Yet another exemplary composition is a mixture of 0053 When used as pesticides or fungicide in their com isobutyric acid, isobutyric anhydride, and caryophyllene. For mercially available formulations and in the use forms pre example, compositions may comprise 20-70% isobutyric pared with these formulations, the active compounds accord acid, 20-70% isobutyric anhydride, and 1-10% caryophyl ing to the invention can furthermore be present in the form of lene. In some embodiments, the composition comprises a mixture with synergists. Synergists are compounds by 30-60% isobutyric acid. In some embodiments, the compo which the activity of the active compounds is increased with sition comprises 30-60% isobutyric anhydride. In sortie out it being necessary for the Synergist added to be active embodiments, the composition comprises 42-53% isobutyric itself. acid, 42-53% isobutyric anhydride, and 3-7% caryophyllene. 0054 When used as pesticides in their commercially For example, the composition can comprise 47.5% isobutyric available formulations and in the use forms prepared with acid, 47.5% isobutyric anhydride, and 5% caryophyllene. these formulations, the active compounds according to the 0049. In yet other embodiments, the composition can invention can furthermore be present in the form of a mixture include, in addition to isobutyric acid and, optionally a deriva with inhibitors which reduce the degradation of the active tive thereof, one or more sesquiterpenes. Such as the sesquit compound after application in the habitat of the plant, on the erpenes present in the VOCs of M. Strobelii. A sesquiterpene Surface of parts of plants or in plant tissues. used in a composition of the invention can be a pheromone, 0055. The active compounds according to the invention, as such as a pheromone that affects the behavior of one or more Such or in their formulations, can also be used as a mixture insect species. For example, sesquiterpene compounds Such with known acaricides, bactericides, fungicides, insecticides, as isocaryophyllene or derivatives thereof (e.g., (-)-tricyclo microbicides, or nematicides, or combinations thereof, for 6.2.1.0(4,11) undec-5-ene, 1.5,9.9-tetramethyl-(isocaryo example in order to widen the spectrum of action or to prevent US 2010/02551 24 A1 Oct. 7, 2010 the development of resistances in this way. In many cases, and in buildings by contacting the building, the building synergistic effects result, i.e. the activity of the mixture can materials, or the spaces between the building materials with exceed the activity of the individual components. A mixture an effective amount of the volatile composition. Further, an with other known active compounds, such as fertilizers, effective amount of the volatile compounds can be used alone growth regulators, safeners and/or semiochemicals is also or in combination with other fumigants in a room or alterna possible. tively, during whole building fumigations. 0056. In a preferred embodiment of the present invention, Treating Plant Pathogens with Volatile Organic Compounds the composition may include at least one of a biological and 0060. The invention further provides a method for treat an additional chemical pesticide. Exemplary chemical pesti ing, inhibiting, or preventing the development of a plant cides include those in the organophosphate, carbamate, orga pathogen disease comprising applying a composition of the nochlorine, and prethroid classes. Also included are chemical invention to a plant, or in the vicinity of the plant prior to or control agents such as, but not limited to, benomyl, borax, concurrent with plant growth. The plant treated according to captafol, captan, chorothalonil, formulations containing cop the methods of the invention can be any type of plant, includ per; formulations containing Zinc, dichlone; dicloran; iodine; ing trees, crop plants, and ornamental plants of any species. fungicides that inhibit ergosterol biosynthesis such as but not Where the composition is applied to the soil or a growth limited to fenarimol, imazalil, myclobutanil, propiconazole, medium, the soil or medium can Support the growth of any prochloraz, terbutrazole, flusilazole, triadimefon, and tebu type of plant. For example, a composition of the invention can conazole; folpet, ipordione; manocoZeb; maneb, metalaxyl; be applied to an oil palm (Elaeisguineensis), coconut (Cocos oxycarboxin, oxytetracycline: PCNB; pentachlorophenol; nucifera), betel (Areca catechu), tea (Camelia sinensis), quinomethionate; sodium aresenite; sodium DNOC: Sodium cocoa (Theobroma cacao), acacia (Acacia species), or poplar hypochlorite; sodium phenylphenate; streptomycin; Sulfur, (Populus species) plant, or soil or a growth medium that thiabendazole; thiophanate-methyl; triforine; Vinclozolin; Supports growth of any of these or other plant species. Zineb., Ziram; tricyclazole; cymoxanil; blastididin; and vali 0061 The composition can be any disclosed herein. In dimycin. Some preferred embodiments, the composition comprises 0057 Exemplary biological pesticides include microbes, isobutyric acid, methyl isobutyrate, and naphthalene. In some animals, plants, bacteria, genetic material, and natural prod embodiments, the composition comprises 20-70% isobutyric ucts of living organisms. For example, fungi that can be acid, 20-70% methylisobutyrate, and 1-10% naphthalene. In combined with a composition that includes isobutyric acid, Some exemplary embodiments, the composition comprises methyl isobutyrate, or isobutyric anhydride, include; without 42-53% isobutyric acid, 42-53% methylisobutyrate, and limitation, Muscodor species, Fusarium lateritium, Metarhi 3-7% naphthalene. Zium aniisopliae ('green muscarine'), Metarhizium flaviride, 0062. In other preferred embodiments, the composition Beauveria bassiana (“white muscarine'), Beauveria brongn comprises isobutyric acid, isobutyric anhydride, and caryo iartii, Chladosporium herbarum, Paecilomyces farinosus, phyllene. In some embodiments, the composition comprises Paecilomyces fumosoroseus, Verticillium lecanii, Hirsutella 20-70% isobutyric acid, 20-70% isobutyric anhydride, and citriformis, Hirsutella thompsoni, Aschersonia aleyrodis, 1-10% caryophyllene. In some exemplary embodiments, the Entomophaga grylli, Entomophaga mainaiga, Ento composition comprises 42-53% isobutyric acid, 42-53% mophaga muscae, Entomophaga praxibulli, Entomophthora isobutyric anhydride, and 3-7% caryophyllene. plutellae, Zoophthora radicans, Neozygitesfloridana, Nomu 0063. The composition can include carriers or other com raea rileyi, Pandora neoaphidis, Tolypociadium cylin pounds that aid in application of the compounds to the plant, drosporum, Culicinomyces clavosporus, Muscodor albus, and/or adherence of the compound to the plant or vicinity of Cordyceps variabilis, Cordyceps facis, Cordyceps, subsessi the plant. For example, the composition can be in the form of lis, Cordyceps myrmecophila, Cordyceps sphecocephala, an emulsion, such as a water-in-oil emulsion, or can be pro Cordyceps entomorrhiza, Cordyceps gracilis, Cordyceps vided with one or more Surfactants, such as an ionic or non militaris, Cordyceps washingtonensis, Cordyceps melolan ionic Surfactant. The composition of Volatile organic com thae, Cordyceps ravenelii, Cordyceps unilateralis, pounds can be provided with a carrier Such as particles or Cordyceps sinensis and Cordyceps clavulata, and mycor powder. Other exemplary carriers include soil, the agricul rhizal species such as Laccaria bicolor. Other mycopesticidal tural and absorbent carriers listed below, and seeds, branches, species will be apparent to those skilled in the art. mulch, and plant fragments that can be spread at the base of 0058 Exemplary food preservatives include antimicrobial the plant. Carriers also include compounds known to those of preservatives, which inhibit the growth of bacteria, and fungi skill in the art that reduce the volatility of the volatile organic and, mold growth, or antioxidants such as oxygen absorbers, compounds during storage, shipment, and plant treatment. which inhibit the oxidation of food constituents. Common Such carriers may be desirable to affect a controlled release of antimicrobial preservatives include calcium propionate, the Volatile organic compounds during plant treatment. Sodium nitrate, sodium nitrite, Sulfites (sulfur dioxide, 0064. In some embodiments, the composition is a liquid Sodium bisulfite, potassium hydrogen Sulfite, etc.) and diso composition, and may be an emulsion, and the composition is dium EDTA. Antioxidants include BHA and BHT. Other used to wipe, water, spray, or drench the plant or areas of the preservatives include formaldehyde (usually in Solution), plant, Such as the roots. Plants, or parts of plants such as the glutaraldehyde (kills insects), ethanol and methylchlor roots, can in Some embodiments be dunked into the compo oisothiazolinone. sition or wrapped in a fabric, fibers, or a filter or matrix that 0059. Using methods well known to those of skill in the contains or is saturated with the composition prior to planting art, the Volatile organic compounds may also be used to or transplanting. In some embodiments, the composition is treating or protecting non-plant materials from fungal or toxic injected into a plant, for example, into the roots, trunk, stems, mold infestations. For example, the Volatile compounds may or leaves. In some embodiments, the Volatile organic com be used to treat or prevent toxic mold on building materials pound composition is watered into the soil. US 2010/02551 24 A1 Oct. 7, 2010

0065. A seed coating or seed dressing formulation can be dahliae, Verticillium dahliae, Xanthomonas axonopodis, applied to the seeds employing the compositions of the inven Xanthomonas Oryzae pv. Oryzae. tion and a diluent in Suitable seed coating formulation form, 0068. In a preferred embodiment of the present invention, e.g. as an aqueous Suspension or in a dry powderform having the application of the Volatile compound composition to the good adherence to the seeds. Such seed coating or seed dress plant results in a reduced occurrence of at least one plant ing formulations are known in the art. Such formulations may disease caused by a bacterium, fungus, or insect as compared contain the single active ingredients or the combination of with plants not treated with the composition. In some embodi active ingredients in encapsulated form, e.g. as slow release ments, the plant disease is caused by Aspergillus fumigatus, capsules or microcapsules. Botrytis cinerea, Cerpospora betae, Curvularia spp., Gano derma bominense, Geotrichum candidum, Mycosphaerella 0066. The composition may be topically administered to fijiensis, Phytophthora palmivora, Phytophthora ramorum, plants, including any or all plant parts, including without Pythium ultimum, Rhizoctonia Solani, Rhizopus spp., Schizo limitation, roots, shoots, stems, bark, leaves, fruit, and/or phyllum spp., Sclerotinia Sclerotiorum, Verticillium dahliae, seeds. For example, the volatile compound composition may or Xanthomonas axonopodis. In a particularly preferred be applied on, in, or near the root of the oil palm. Single and embodiment of the invention, the host plant is susceptible to multiple applications are contemplated. Multiple applica diseases caused by Ganoderma bominense. In another pre tions can be through more than one application method. ferred embodiment, the host plant is an oil palm plant. In other 0067. The compositions of the invention are particularly preferred embodiments, the disclosed compositions and useful in combating plant pests and plant pathogens, particu methods are effective to kill the plant pathogen. larly phytopathogenic fungi. Thus, the invention has may be 0069. It is understood that all plants and plant parts can be used to treat, inhibit or prevent the development of plant treated in accordance with the invention. Plants are to be pathogenic diseases caused by a broad range of fungi. The understood as meaning in the present context all plants and compositions and methods of the present invention are pref plant populations such as desired and undesired wild plants or erably used against fungi that are important or interesting for crop plants (including naturally occurring crop plants). Crop agriculture, horticulture, plant biomass for the production of plants can be plants which can be obtained by conventional biofuel molecules and other chemicals, and/or forestry. Non plant breeding and optimization methods or by biotechno limiting examples include, for instance, Acremonium stric logical and recombinant methods or by combinations of these tum, Agrobacterium tumefaciens, Alternaria alternata, Alter methods, including the transgenic plants and plant cultivars naria Solani, Aphanomyces euteiches, Aspergillus fumigatus, protectable or not protectable by plant breeders rights. Plant Athelia rolfsii, Aureobasidium pullulans, Bipolaris Zeicola, parts are to be understood as meaning all parts and organs of Botrytis cinerea, Calonectria kyotensis, Cephalosporium plants above and below the ground, Such as shoots leaf flower maydis, Cercospora medicaginis, Cercospora Sojina, Colle and root, examples which may be mentioned being leaves, totrichum coccodes, Colletotrichum fragariae, Colletotri needles, stalks, stems, flowers, fruit bodies, fruits, seeds, chum graminicola, Coniella diplodiella, Coprinopsis psy roots, tubers and rhizomes. The plant parts also include har chromorbida, Corynespora cassicola, Curvularia Vested material, and vegetative and generative propagation pallescens, Cylindrocladium Crotalariae, Diplocarpon ear material, for example cuttings, tubers, rhizomes, offsets and lianum, Diplodia gossvina, Diplodia spp., Epicoccum seeds. nigrum, Erysiphe cichoracearum, Fusarium graminearum, 0070. As discussed above, the compositions and methods Fusarium oxysporum, Fusarium oxysporum f.sp. tuberosi, according to the present invention in principle can be applied Fusarium proliferatum var. proliferatum, Fusarium Solani, to any plant. Therefore, monocotyledonous as well as dicoty Fusarium verticillioides, Ganoderma bominense, Geotri ledonous plant species are particularly Suitable. The process chum candidum, Glomerella tucumanensis, Guignardia bid is preferably used with plants that are important or interesting welli, Kabatiella zeae, Leptosphaerulina briosiana, Lep for agriculture, horticulture, for the production of biomass totrochila rmedicaginis, Macrophomina, Macrophomina used in producing liquid fuel molecules and other chemicals, phaseolina, Magnaporthe grisea, Magnaporthe Oryzae, and/or forestry. Microsphaera manshurica, Monilinia fructicola, 0071. Thus, the invention has use over a broad range of Mycosphaerella fijiensis, Mycosphaerella fragariae, plants, preferably higher plants pertaining to the classes of Nigrospora Oryzae, Ophiostoma ulmi, Pectobacterium caro Angiospermae and Gymnospermae. Plants of the Subclasses tovorum, Pellicularia Sasakii (Rhizoctonia Solani), Perono of the Dicotylodenae and the Monocotyledonae are particu spora manshurica, Phakopsora pachyrhizi, Phoma foveata, larly suitable. Dicotyledonous plants belong to the orders of Phoma medicaginis, Phomopsis longicolla, Phytophthora the Magniolales, Illiciales, Laurales, Piperales Aristochi cinnamomi, Phytophthora erythroSeptica, Phytophthora ales, Nymphaeaks, Ranunculales, Papeverales, Sarraceni fragariae, Phytophthora infestans, Phytophthora medicagi aceae, Trochodendrales, Hamamelidales, Eucomiales, Leit nis, Phytophthora megasperma, Phytophthora palmivora, neriales, Myricales, Fagales, Casuarinales, Caryophyllales, Podosphaera leucotricha, Pseudopeziza medicaginis, Puc Batales, Polygonales, Plumbaginales, Dilleniales, Theales, cinia graminis subsp. Tritici (UG99), Puccinia sorghi, Malvales, Urticales, Lecythidales, Violales, Salicaks, Cappa Pyricularia grisea, Pyricularia Oryzae, Pythium ultimum, rales, Ericales, Diapensales, Ebenales, Primulales, Rosales, Rhizoctonia Solani, Rhizoctonia zeae, Rosellinia sp., Sclero Fabales, Podostemales, Haloragales, Myrtales, Cornales, tinia sclerotiorum, Sclerotinina trifoliorum, Sclerotium rolf Proteales, Santales, Rafflesiales, Celastrales, Euphorbiales, sii, Septoria glycines, Septoria lycoperski, Setomelanomma Rhamnales, Sapindales, Juglandales, Geraniales, Polygala turcica, Sphaerotheca macularis, Spongospora subterranea, les, Umbellales, Gentianales, Polemoniales, Lamiales, Plan Stemphylium sp., Synchytrium endobioticum, Thecaphora taginales, Scrophulariales, Campanulales, Rubiales, Dipsa (Angiosorus). Thielaviopsis, Tilletia indica, Trichoderma cales, and Asterales. Monocotyledonous plants belong to the viride, Ustilago maydis, Verticillium albo-atrum, Verticillium orders of the Alismatales, Hydrocharitales, Najadales, Triu US 2010/02551 24 A1 Oct. 7, 2010

ridales, Commelinales, Eriocaulales, Restionales, Poales, male, Veratrum Califormica, Digitalis lanata, Digitalis pur Juncales, Cyperales, Tiphales, Bromeliales, Zingiberales, purea, Dioscorea spp., Andrographis paniculata, Atropa bel Arecales, Cyclanthales, Pandanales, Arales, Lilliales, and ladonna, Datura Stonominium, Berberis spp., Cephalotaxus Orchidales. Plants belonging, to the class of the Gymnosper spp., Ephedra sinica, Ephedra spp., Erythroxylum coca, Gal mae are Pinales, Ginkgoales, Cycadales and Gnetales. anthus wormorii, Scopolia spp., Lycopodium serratum (Hu 0072 Suitable species may include members of the genus perzia serrata), Lycopodium spp., Rauwolfia serpentina, Abelmoschus, Abies, Acer; Agrostis, Allium, Alstroeneria, Rauwolfia spp., Sanguinaria Canadensis, Hyoscyamus spp., Ananas, Andrographis, Andropogon, Artemisia, Arundo, Calendula officinally, Chrysanthemum parthenium, Coleus Atropa, Berberis, Beta, Bixa, Brassica, Calendula, Camelia, forskohli, Tanacetum parthenium, Parthenium argentatum Camptotheca, Cannabis, Capsicum, Carthamus, Catharan (guayule), Hevea spp. (rubber), Mentha spicata (mint), Men thus, Cephalotaxus, Chrysanthemum, Cinchona, Citrullus, tha piperita (mint), Bixa Orellana, Alstroemeria spp., Rosa Coffea, Colchicum, Coleus, Cucumis, Cucurbita, Cynodon, spp. (rose), Dianthus caryophyllus (carnation), Petunia spp. Datura, Dianthus, Digitalis, Dioscorea, Elaeis, Ephedra, (petunia), Poinsettia pulleherrima (poinsettia), Nicotiana Erianthus, Erythroxylum, Eucalyptus, Festuca, Fragaria, tabacum (tobacco); Lupinus albus (lupin), Uniola paniculata Galanthus, Glycine, Gossypium, Helianthus, Hevea, Hor (oats), bentgrass (Agrostis spp.), Populus tremuloides (as deum, Hyoscyamus, Jatropha, Lactuca, Linum, Lolium, Lupi pen), Pinus spp. (pine), Abies spp. (fir), Acer spp. (maple), nus, Lycopersicon, Lycopodium, Manihot, Medicago, Men Hordeum, vulgare (barley), Poa pratensis (bluegrass), Lolium tha, Miscanthus, Musa, Nicotiana, Oryza, Panicum, Papover, spp. (ryegrass), Phleum pratense (timothy), and conifers. Of Parthenium, Pennisetum, Petunia, Phalaris, Phkum, Pinus, Poa, Poinsettia, Populus, Rauwolfia, Ricinus, Rosa, Saccha interest are plants grown for energy production, so called rum, Salix, Sanguinaria, Scopolia, Secale, Solanum, Sor energy crops, such as tellulose-based energy crops like Pani ghum, Spartina, Spinacea, Tanacetum, Taxus, Theobroma, cum virgatum (Switchgrass), Sorghum bicolor (Sorghum, Triticosecale, Triticum, Uniola, Veratrum, Vinca, Vitis, and Sudangrass), Miscanthus giganteus (miscanthus), Saccharum Zea. sp. (energycane), Populus balsamifera (poplar), Andropogon 0073. The methods of the present invention are preferably gerardii (big bluestem), Pennisetum purpureum (elephant used in plants that are important or interesting for agriculture, grass), Phalaris arundinacea (reed canarygrass), Cynodon horticulture, biomass for the production of biofuel Molecules dactylon (bermudagrass), Festuca arundinacea (tall fescue), and other chemicals, and/or forestry. Non-limiting examples Spartina pectinata (prairie cord-grass), Medicago sativa (al include, for instance, Panicum virgatum (switchgrass), Sor falfa), Arundo donax (giant reed), Secale cereale (rye), Salix ghum bicolor (Sorghum, Sudangrass), Miscanthus giganteus spp. (willow), Eucalyptus spp., (eucalyptus), Triticosecale (miscanthus), Saccharum sp. (energycane), Populus balsam spp. (triticum-wheat X rye), and Bamboo; and starch-based ifera (poplar), Zea mays (corn), Glycine max (soybean), Bras energy crops like Zea mays (corn) and Manihot esculenta sica napus (canola), Triticum aestivum (wheat), Gossypium (cassaya); and Sucrose-based energy crops like Saccharum hirsutum (cotton), Oryza sativa (rice), Helianthus annuus sp. (Sugarcane) and Beta vulgaris (Sugarbeet); and biofuel (Sunflower), Medicago sativa (alfalfa), Beta vulgaris (Sugar producing energy crops like Glycine max (soybean), Brassica beet), Pennisetum glaucum (pearl millet), Panicum spp., Sor napus (canola), Helianthus annuus (Sunflower), Carthamus ghum spp., Miscanthus spp., Saccharum spp., Erianthus spp., tinctorius (safflower), Jatropha curcas (Jatropha), Ricinus Populus spp., Andropogon gerardii (big bluestem), Pennis communis (castor), Elaeis guineensis (African oil palm), etum purpureum (elephant grass), Phalaris arundinacea Elaeis oleifera (American oil palm), Cocos nucifera (coco (reed canarygrass), Cynodon dactylon (bermudagrass), Fes nut), Camelina sativa (wild flax), Pongamia pinnata (Pon tuca arundinacea (tal fescue), Spartina pectinata (prairie gam), Olea europaea (olive), Linum usitatissimum (flax), cord-grass), Arundo donax (giant reed), Secale cereale (rye), Crambe abyssinica (Abyssinian-kale), and Brassica iuncea. Salix spp. (willow), Eucalyptus spp. (eucalyptus), Triticose Treatment of Soil with Volatile Organic Compounds cale spp. (triticum wheatX rye), Bamboo, Carthamus tinc 0074 The invention provides for a method to treat soil or torius (safflower), Jatropha curcas (Jatropha), Ricinus Com other similar plant growth media with compositions of the munis (castor), Elaeis guineensis (oil palm), Phoenix present invention. The invention provides a method to use dactylifera (date palm), ArchOntophoenix cunninghamiana compositions as disclosed herein to kill plant pathogens in (king palm), Syagrus romanzofiana (queen palm), Linum soil. Typically; the composition comprises two or more Vola usitatissimum (flax), Brassica iuncea, Manihot esculenta tile organic compounds and, optionally, an agricultural car (cassaya), Lycopersicon esculention (tomato), Lactuca saliva rier. Carriers in some embodiments reduce loss of the volatile (lettuce), Musa paradisiaca (banana), Solanum tuberosum organic compounds during application. In some embodi (potato), Brassica oleracea (broccoli, cauliflower, brussel ments, the carriers are absorbent materials that can be soaked sprouts), Camelia sinensis (tea), Fragaria ananassa (Straw in or permeated with the composition, such that the absorbent berry), Theobroma cacao (cocoa), Coffea arabica (Coffee), material can hold and prevent immediate Volatilization and Vilis vinifera (grape), Ananas Comosus (pineapple), Capsi diffusion of the compounds of the composition. Once mixed cum annum (hot & Sweet pepper), Allium, cepa (onion), with the soil, the carrier can allow more gradual release of the Cucumis melo (melon), Cucumis sativus (cucumber), Cucur Volatile compounds through the soil. Examples of Such car bita maxima (squash), Cucurbita moschata (squash), riers include, without limitation, peat, humus, Vermiculite, Spinaceca oleracea (spinach), Citrullus lanatus (water shredded paper, paper, fabric, or wood fibers from waste or melon), Abelmoschus esculentus (okra), Solanum melongena recycling processes, sawdust, ground of pulverized Sugar (eggplant), Papaver SOmniferuin (opium poppy), Papaver bagasse, grain husks, or empty fruit bunches, etc. Other agri Orientale, Taxus baccata, Taxus brevifolia, Artemisia annua, cultural carriers include seeds, branches, mulch, plant frag Cannabis saliva, Camptotheca acuminate, Catharanthus ments, and powdered milk. One agricultural carrier is soil roseus, Vinca rosea, Cinchona officinalis, Coichicum autum itself. The soil or plant growth media may be treated prior to US 2010/02551 24 A1 Oct. 7, 2010

(e.g., a sterilization treatment before planting) or concurrent the art upon review of this disclosure. The following with plant growth (e.g., a treatment while planting, or after examples are offered to illustrate, but not limit, the invention. growth is established). 0075. The volatile organic compounds are added to the Example 1 soil. Mixing may then be performed to distribute the com pounds throughout the vicinity of the target plant pathogen. In uantitative Analysisy of Volatile Organic9. Com other embodiments, the Volatile compound composition is pounds (VOCs) from Muscodor strobelii mixed directly with the soil in the absence of a solid or particulate carrier. I0082. The gases in the air space above a 14 day old culture 0076. In yet other embodiments, the composition is of the MB-8 Muscodor strobelii growing on a Petri plate injected into the soil. For example, a composition that (PDA) were quantitatively analyzed (live culture deposited includes isobutyric acid, methyl isobutyrate, or butyric anhy on Jun. 5, 2009 in the Agricultural Research Culture Collec dride can be provided in a vessel under pressure, and can be tion located at 1815 N. University Street, Peoria, Ill. 61604, injected about one, two, three, four, five, six, seven, eight, USA (NRRL) in accordance with the Budapest Treaty on the nine, ten, between ten and fifteen, or between fifteen and International Recognition of the Deposit of Microorganisms twenty centimeters, between twenty and thirty centimeters, for the Purpose of patent Procedure and the Regulations between thirty and fifty centimeters, or further below the thereunder (Budapest Treaty) as Accession Number NRRL Surface of the soil at intervals throughout an area that is 50288). First, a baked “Solid Phase Micro Extraction” planted with a plant species of interest, or will be planted with syringe (Supelco) consisting of 50/30 divinylbenzene/carbu a plant species of interest. In some embodiments, the soil is ren on polydimethylsiloxane on a stable flex fiber was placed covered after-injection of the composition to reduce loss of through a small hole drilled in the side of the Petri plate the Volatile compound. For example, plastic sheeting can be sporting the growth of MB8. The fiber was exposed to the used to cover the injected area so that it remains covered for vapor phase of the fungus for 45 minutes. The Syringe was from about eight hours to about one month after injection. then inserted into the splitless injection port of a Hewlett 0077. The treated soil may be then used for planting of Packard 6890 gas chromatograph containing a 30 mx0.25 plants susceptible to pathogens that can be effectively inhib mm I.D. ZB Wax capillary column with a film thickness of ited or killed by the volatile organic compounds. In some 0.50 mm. The column was temperature programmed as fol embodiments, soil or plant growth medium is treated where lows: 30° C. for 2 minutes followed to 220° C. at 5° plants have already been planted or established in the soil or C./minute. The carrier gas was ultra high purity Helium (local growth medium. Volatile organic compounds may also be distributor), and the initial column head pressure was 50 kPa. topically administered to plants, including all plant parts, Prior to trapping the volatiles, the fiber was conditioned at specifically on, in, or near the roots of the oil palm. In some 240° C. for 20 minutes under a flow of helium gas. A 30 embodiments, Soil may be treated while plants are growing in second injection time was used to introduce the sample fiber the soil. into the GC. The gas chromatograph was interfaced to a 0078. In yet other embodiments, a compound of the inven Hewlett. Packard 5973 mass selective detector (mass spec tion is watered into the Soil from an irrigation system, for trometer) operating at unit resolution. Data acquisition and example, a spray or drip irrigation system. data processing were performed on the Hewlett Packard 007.9 The composition with soil or an agricultural carrier ChemStation software system. Initial identification of the may also be applied to the base of oil palm plants. The unknowns produced by MB8 was made through library com composition may also be directly applied to the roots of the parison using the NIST database. The identified compounds plants. The plants may have root disease caused by a plant and their peak areas are provided in Table 2. pathogen. The plant pathogen may be Ganoderma bominense. Other exemplary plant pathogens causing root diseases TABLE 2 include Phytophthora palmivora, Pythium ultimum, or Scle VOCs produced by a 14 day old culture rotinia Sclerotiorum. It is desired that the Volatile organic of Muscodor strobei on PDA. compounds inhibit growth of or kill plant pathogenic fungi Retention Peak Such as Ganoderma bominense, Phytophthora palmivora, Time Area Possible Compound MW Pythium ultimum, and Sclerotinia Sclerotiorum. 3.853 6.07 Acetone 58 0080. Another aspect of the invention provides a method 4.287 2.28 2-Butanone 72 for Screening microbial strains that may be useful for treating, 4.887 33.13 Isobutyric acid, methyl ester O2 inhibiting, or preventing the development of a plant patho S.682 122.88 Isobutyric acid 88 genic disease. The method involves (i) exposing or contacting S.740 3.77 Methyl 2-methoxypropenoate 16 S.903 2.29 Acetic acid, (tert-butylthio)- 48 candidate microbial strains with the invention composition, 6.389 2.86 2-Methylheptanoic acid 44 (ii) selecting microbial Strains resistant to the composition, 6.504 0.35 Methyl 2,3-dimethylbutanoate 30 and (iii) characterizing the selected microbial strain. The 6.961 11.04 Allyl 2-methylpropanoate 28 characterization of the selected microbial Strains can be car (isobutyric anhydride) 7.512 1.13 N,2-dimethylpropanamide O1 ried by a variety of known molecular and microscopy tech 9.090 0.39 Heptyl allyl oxalate 228 niques. Non-limiting examples of Such techniques include 9.931 0.26 Butyl propyl oxalate 88 electron microscopy, GC-MS analysis of VOC profile, PCR 10.012 0.22 1-(ethenyloxy)-3-methyl-butane 14 amplification and phylogenetic analysis of the 18S or the 11.278 2.94 alpha-Gurjunene 204 11.332 2.15 (-)-Aristolene 204 ITS-5.8S rDNA sequences. 11436 1.07 alpha-Patchoulene 204 0081. The discussion of the general methods given herein 11.557 6.28 4,5-dimethyl-1,2,3,6,7,8,8a,8b- 88 is intended for illustrative purposes only. Other alternative octahydrobiphenylene methods and embodiments will be apparent to those skilled in US 2010/02551 24 A1 Oct. 7, 2010 10

TABLE 2-continued TABLE 3-continued VOCs produced by a 14 day old culture Exemplary Plant Essential Oils. of Muscodor strobei on PDA. eugenol Retention Peak fennel oil Time Area Possible Compound MW geraniol ginger oil 11.740 14.91 (-)-tricyclo6.2.1.0(4.11) undec-5- 204 jojoba oil ene, 1.5.9.9-tetramethyl-(isocaryophyllene-II) lemongrass oil 11.929 0.44 pentamethyl-benzene 148 limonene 12.032 0.74 Bergamotene 204 linalool 12.099 0.14 44-diethyl-2,5-octadiyne 162 patchouli oil 12.190 0.34 2-(1-Propenyl)-6-methylphenol 148 peppermint oil 12446 0.06 (Z)-7,11-dimethyl-3-methylene-1,6,10- 204 C-terpinene dodecatriene rosemary oil 12.683 0.86 4.5-dehydro-isolongifolene 2O2 tea tree oil thyme oil

Example 2 I0086 A mixture of 47.5% isobutyric acid: 47.5% isobu tyric anhydride; and 5% caryophyllene was placed in a small Use of Compositions of Volatile Organic Com cup in the center of a Petri plate with potato dextrose agar pounds to Kill Plant Pathogens (PDA) and tested for activity on fungal as described above. 0083. A composition containing a mixture of volatile The results showed that Ganoderma bominense and Pythium compounds was prepared as follows: 47.5% isobutyric, acid, ultimum and Phytophthora palmivora were also each killed 47.5% methyl ester of isobutyric acid (methyl isobutyrate), by this mixture of volatile compounds. and 5% naphthalene. 0087. To determine the effectiveness of individual com 0084. To test the bioactivity, the mixture was placed in a ponents of the tested VOC mixtures in killing pathogenic small cup in the center of a Petri plate with potato dextrose fungi, isobutyric acid and methyl isobutyrate were also tested agar (PDA) (Strobel et al., 2001 Microbiology 147: 2943 on their own. In one experiment, isobutyric acid was placed in 2950). The volumes of liquid tested were 0, 2.5, 5.0, 10.0 and a small cup in the center of a Petri plate with potato dextrose 20 microliters as per Strobel et al., supra. Then small cubes of agar (PDA) and tested for activity on fungi as described fungal inoculum grown on PDA were also applied to the above. The results showed that the growth of each of Gano plate. The plates were sealed with parafilm and incubated for derma bominense and Pythium ultimum and Phytophthora 3 days, at which time measurements of hyphal development palmivora was inhibited by isobutyric acid alone, but not were made. Also, after 3 days the Small plug of fungal inocu killed even at the higher concentrations. lum was removed from the plate and transferred to a fresh I0088. In another experiment, the methyl ester of isobutyric PDA plate to determine if the test fungus was still alive acid (methyl isobutyrate) was placed in a small cup in the (capable of growth) and this was recorded. The results center of a Petri plate with potato dextrose agar (PDA) and showed that Ganoderma bominense and Pythium ultimum and tested for activity on fungi as described above. The results Phytophthora palmivora were each killed by the lethal mix showed no growth inhibition of Ganoderma bominense and ture of Volatile compounds. Pythium ultimum or, Phytophthora palmivora occurred with 0085. In another experiment, a composition containing a methyl isobutyrate alone, even at the higher concentrations. mixture of Volatile compounds that included caryophyllene was tested for its ability to inhibit the growth of fungal patho Example 3 gens. Caryophyllene is a sesquiterpene VOC that is found in products of certain plants, for example, essential oils such as Use of Compositions of Volatile Organic Com clove oil. Additional examples of plant essential oils that can pounds to Kill Ganoderma bominense in Soil be present in a composition of the invention are provided in Table 3. I0089. Since the composition of Example 2 effectively killed Ganoderma bominense, 50 ul of the test mixture of TABLE 3 Example 2 (47.5% isobutyric acid, 47.5% methyl ester of isobutyric acid (methyl isobutyrate), and 5% naphthalene) Exemplary Plant Essential Oils. was applied to the base of a 5 ml sterile plastic tube containing basil oil autoclaved Malaysian Sandy loam (from an oil palm planta black pepper oil tion). The loam mixture had been inoculated with diced agar (-)-camphor blocks containing a fresh culture of Ganoderma bominense carvacrol trans-cinnamaldehyde which was equivalent to 0.5 mg dry weight of fungus myce cinnamon leaf oil lium. A control tube containing no artificial mixture was also cinnamon bark oil set up. Both were incubated for three days and then plated on citronellol PDA. There was no fungal growth on the treated soil (plate on citral the right in FIG. 1), but on the control there was enormous (+)-citronellal clove bud oil growth of Ganoderma bominense (plate on the left in FIG. 1). eucalyptol The conclusion was that the VOC mixture had completely and eucalyptus oil effectively killed all hyphae of Ganoderma bominense that had been placed in the soil. US 2010/02551 24 A1 Oct. 7, 2010

0090. A number of embodiments of the invention have 11. A composition according to claims 1, wherein the com been described. Nevertheless, it will be understood that, ele position is in the form of a powder, a granule, a pellet, a gel. ments of the embodiments described herein can be combined an aqueous Suspension, a solution, or an emulsion. to make additional embodiments and various modifications 12. A composition according to claim 1, wherein the com may be made without departing from the spirit and scope of position further comprises a carrier. the invention. Accordingly, other embodiments, alternatives 13. A composition according to claim 12, wherein the and equivalents are within the scope of the invention and carrier is an agriculturally acceptable carrier. claimed herein. Headings within the application are solely for 14. The composition according to claim 12, wherein the the convenience of the reader, and do not limit any way the carrier is a seed. Scope of the invention or its embodiments. 0091 All, publications and patent applications mentioned 15. A method for treating; inhibiting or preventing the in this specification are herein incorporated by reference to development of a plant pathogenic disease, wherein said the same extent as if each individual publication or patent method comprises applying a composition according to claim application was specifically can individually indicated to be 1 in the vicinity of a host plant. incorporated by reference. 16. A method according to claim 15, wherein the pathogen What is claimed is: is selected from the group consisting of Aspergillus filmiga 1. A composition for treating; inhibiting or preventing the tus, Botrytis cinerea, Cerpospora betae, Curvularia sp., development of a plant pathogenic disease, wherein said Ganoderma bominense, Geotrichum candidum, Mycosphaer composition comprises two or more compounds, wherein the ella fijiensis, Phytophthora palmivora, Phytophthora first of said two or more compounds is selected from the ramorum, Pythium ultimurn, Rhizoctonia Solani, Rhizopus group consisting of isobutyric acid, methyl isobutyrate and sp., Schizophyllum sp., Sclerotinia Sclerotiorum, Verticillium isobutyric anhydride; and wherein the second of said two or dahliae, and Xanthomonas axonopodis. more compounds is selected from the group consisting of 17. A method according to claim 15, wherein the host, plant isobutyric acid, methyl isobutyrate, isobutyric anhydride, is susceptible to Ganoderma bominense. ethyl isobutyrate, propyl isobutyrate, isobutyric acid-allyl 18. A method according to claim 15, wherein the host plant ester, naphthalene, caryophyllene, and a plant essential oil. is an oil palm plant. 2. A composition according to claim 1, wherein the com 19. A method according to claim 15, wherein the compo position comprises isobutyric acid. sition is applied in the vicinity of or onto the roots, stems, 3. A composition according to claim 2, wherein the com trunk, seed, or leaves of the host plant. position further comprises naphthalene, caryophyllene or a 20. A method according to claim 15, wherein the compo plant essential oil. 4. A composition according to claim 2, wherein the com sition is injected into the roots, stems, trunk, seed, or leaves of position further comprises isobutyric anhydride or methyl the host plant. isobutyrate. 21. A method for treating, inhibiting or preventing the 5. A composition according to claim 4, wherein the com development of a plant pathogenic disease, said method com position further comprises naphthalene, caryophyllene or a prising exposing or contacting the growth medium of a host plant essential oil. plant to or with the composition of claim 1 prior to or con 6. A composition according to claim 1, wherein the com current with plant growth in said growth medium. position comprises isobutyric anhydride or methyl isobu 22. A method for screening microbial strains, said method tyrate. comprising (i) exposing or contacting candidate microbial 7. A composition according to claim 6, wherein the com strains with a composition according to claim 1, (ii) selecting position further comprises naphthalene, caryophyllene or a microbial strains resistant to the composition, and (iii) char plant essential oil. acterizing the selected microbial strain; wherein said method 8. A composition according to claim 4, wherein the com identifies a microbial strain useful for treating, inhibiting or position comprises 20-70% isobutyric acid and 20-70% preventing the development of a plant pathogenic disease. isobutyric anhydride. 23. An isolated microbial strain obtainable by the method 9. A composition according to claim 8, wherein the com according to claim 22. position further comprises 1-10% naphthalene, caryophyl 24. A method for killing, inhibiting or preventing the devel lene or a plant essential oil. opment of an organism selected from the group consisting of 10. A composition according to claim 1, wherein the com a fungus, a bacterium, a microorganism, a nematode, and an position further comprises an agriculturally effective amount insect; wherein said method comprises exposing or contact of a pesticidal compound or composition selected from the ing the organism to or with an effective amount of a compo group consisting of anacaricide, a bactericide, a fungicide, an sition according to claim 1. insecticide, a microbicide, a nematicide, and a food preser vative. c c c c c