Agricultural composition for controlling and/or treating vascular tissue diseases of plants

文档序号:1908989 发布日期:2021-11-30 浏览:27次 中文

阅读说明:本技术 用于控制和/或治疗植物的维管组织病害的农业组合物 (Agricultural composition for controlling and/or treating vascular tissue diseases of plants ) 是由 P·S·博格 L·C·C·卡弗坎特 M·阿松桑 于 2020-02-19 设计创作,主要内容包括:本发明涉及包含单宁酸的农业组合物和/或佐剂和/或罐式混合物,以控制和/或处理和/或逆转与植物相关的病害或缺陷的症状,特别是与植物的维管和其他组织相关的病害或缺陷的症状。本发明还包括用于控制和/或处理植物的维管病害的方法。(The present invention relates to agricultural compositions and/or adjuvants and/or tank mixes comprising tannic acid to control and/or treat and/or reverse the symptoms of diseases or defects associated with plants, particularly diseases or defects associated with vascular and other tissues of plants. The invention also includes methods for controlling and/or treating vascular disease in plants.)

1. A method for controlling and/or treating vascular disease in a plant, the method comprising the steps of: applying an agricultural composition comprising tannic acid to a plant in need thereof.

2. The method of claim 1, wherein the pesticide composition further comprises a nutrient compound provided as a fertilizer component, wherein the fertilizer component comprises at least one of the following group elements: nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), boron (B), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silicon (Si), or zinc (Zn).

3. The method of claim 1 wherein the agricultural composition further comprises a nutrient compound in the form of monoethanolamine borate.

4. A method according to any one of claims 1 to 3 wherein the agricultural composition further comprises an adjuvant prior to application to the plant.

5. As claimed in claim 4The method of (a), wherein the adjuvant comprises at least one anionic surfactant, wherein the at least one anionic surfactant is selected from the group consisting of: (C)6–C18) Alkyl benzene sulfonate, calcium dodecyl benzene sulfonate, sodium alkyl benzene sulfonate, and amine (C)6–C18) Alkyl benzene sulfonate, trihydroxyethyl amine dodecyl benzene sulfonate and (C)6–C18) Alkyl ether sulfates, (C)6–C18) Alkyl ethoxylated ether sulfates (C)6–C18) Alkyl sulfate, sodium lauryl ether polyethoxylate sulfate and (C)6–C18) Alkyl phosphate, (C)6–C18) Alkoxylated sulfates, (C)6–C18) Alkoxylated phosphate esters, xylene sulfonates, cumene sulfonates, and combinations thereof.

6. The method of claim 5, wherein the adjuvant further comprises at least one nonionic surfactant selected from the group consisting of: natural and/or synthetic (C)8–C22) Alkoxylated fatty alcohols, (C)8–C22) Ethoxylated fatty alcohols, (C)8–C22) Propoxylated fatty alcohols, (C)8–C22) Ethoxylated and propoxylated fatty alcohols, straight chain (C)4–C10) Alkyl (poly) glycosides, branched chains (C)4–C10) Alkyl (poly) glycosides; and fatty acid alkoxylated sorbitan esters, fatty acid alkoxylated sorbitol esters, fatty acid ethoxylated sorbitan esters, fatty acid ethoxylated sorbitol esters, monolaurate polyethylene glycol sorbitan esters, monopalmitoate polyethylene glycol sorbitan esters, monostearate polyethylene glycol sorbitan esters, and combinations thereof.

7. The method of any one of claims 1 to 6, wherein prior to application to the plant, the agricultural composition further comprises an additive selected from the group consisting of: preservatives, clarifiers, antifreeze agents, hydrotropes, stabilizers, antioxidants, acidulants, chelates, complexing agents, dyes, rheology modifiers, defoamers, anti-drift and water repellents, oils or other solvents, and combinations thereof.

8. The method of any one of claims 1 to 7, wherein the agricultural composition further comprises at least one essential oil selected from the group consisting of: natural oils and synthetic oils, wherein the natural oils consist of terpene oils, including citrus oils.

9. The method of any one of claims 1 to 8, wherein the agricultural composition further comprises water and is formulated as a liquid prior to application to the plant, and the agricultural composition is formulated as a liquid selected from the group consisting of: solutions, concentrated solutions, dilutions, aqueous solutions, aqueous suspensions, liquid extracts, liquid creams, liquid concentrates, suspensions, concentrated suspensions, microcapsule suspensions, pastes, liquid pastes, paste concentrates, slurries, water-dispersed slurries, gels, liquid-soluble gels, and combinations thereof.

10. The method of claim 1, wherein the agricultural composition is formulated as a solid selected from the group consisting of: water dispersible powders, water soluble powders, dustable powders, floating powders, crystals, granules, water dispersible granules, water soluble granules, encapsulated granules, fine granules, microgranules, self-dispersing floating granules, capsules, microcapsules, pellets, dispersible concentrates, dry flowable, water dispersible pellets, water soluble pellets, tablets, water dispersible tablets, briquettes, flakes, and combinations thereof.

11. The method according to any one of claims 1 to 10, wherein the vascular disease of the plant is citrus greening disease or Huanglongbing (HLB).

12. A liquid agricultural adjuvant for controlling and/or treating vascular diseases in plants, the liquid agricultural adjuvant comprising:

at least one essential oil;

at least one anionic surfactant;

at least one nonionic surfactant; and

tannic acid.

13. The liquid agricultural adjuvant of claim 12 having from about 0.1% to about 20% by weight of at least one essential oil, from about 0.1% to about 25% by weight of tannic acid, the presence of at least one anionic surfactant in an amount from about 1% to about 50% by weight, and the presence of at least one nonionic surfactant in an amount from about 1% to about 50% by weight, wherein the liquid agricultural adjuvant is provided in a concentrated form.

14. A liquid agricultural adjuvant according to claim 13 further comprising from about 0.1% to about 80% of a nutrient compound provided as a fertilizer component, wherein the fertilizer component comprises at least one of the following group elements: nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), boron (B), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silicon (Si), or zinc (Zn).

15. A liquid agricultural adjuvant according to claim 14 wherein the fertilizer component is monoethanolamine borate.

16. A liquid agricultural adjuvant according to any one of claims 12 to 15 wherein at least one essential oil is selected from the group consisting of: natural oils and synthetic oils, wherein the natural oils consist of terpene oils, including citrus oils.

17. A liquid agricultural adjuvant according to any one of claims 12 to 16 wherein at least one anionic surfactant is selected from the group consisting of: (C)6–C18) Alkyl benzene sulfonate, calcium dodecyl benzene sulfonate, sodium alkyl benzene sulfonate, and amine (C)6–C18) Alkyl benzene sulfonate, trihydroxyethyl amine dodecyl benzene sulfonate and (C)6–C18) Alkyl ether sulfates, (C)6–C18) Alkyl ethoxylated ether sulfates (C)6–C18) Alkyl sulfate, sodium lauryl ether polyethoxylate sulfate and (C)6–C18) Alkyl phosphate, (C)6–C18) Alkoxylated sulfates, (C)6–C18) Alkoxylated phosphate esters, xylene sulfonates, cumene sulfonates, and combinations thereof.

18. A liquid agricultural adjuvant according to claim 17 wherein at least one non-ionic surfactant is selected from the group consisting of: natural and/or synthetic (C)8–C22) Alkoxylated fatty alcohols, (C)8–C22) Ethoxylated fatty alcohols, (C)8–C22) Propoxylated fatty alcohols, (C)8–C22) Ethoxylated and propoxylated fatty alcohols, straight chain (C)4–C10) Alkyl (poly) glycosides, branched chains (C)4–C10) Alkyl (poly) glycosides; and fatty acid alkoxylated sorbitan esters, fatty acid alkoxylated sorbitol esters, fatty acid ethoxylated sorbitan esters, fatty acid ethoxylated sorbitol esters, monolaurate polyethylene glycol sorbitan esters, monopalmitoate polyethylene glycol sorbitan esters, monostearate polyethylene glycol sorbitan esters, and combinations thereof.

19. A liquid agricultural adjuvant according to any one of claims 12 to 18 further comprising at least one additive selected from the group consisting of: preservatives, clarifiers, antifreeze agents, hydrotropes, stabilizers, antioxidants, acidulants, chelates, complexing agents, dyes, rheology modifiers, defoamers, anti-drift and water repellents, oils or other solvents, and combinations thereof.

20. A pot mix comprising water for application to plants to control and/or treat vascular disease, the pot mix comprising 0.1 to 25 wt% tannic acid, wherein the pot mix is formulated such that when applied to a plant, tannic acid is applied at 0.1 to 1.5 kg/ha or 0.1 to 1.5 l/ha.

21. An agricultural composition comprising tannic acid for controlling and/or treating vascular tissue disease in plants.

22. The agricultural composition of claim 21, further comprising a nutrient compound provided as a fertilizer component, wherein the fertilizer component comprises at least one of the following group elements: nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), boron (B), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silicon (Si), or zinc (Zn).

23. The agricultural composition of claim 21 further comprising a nutrient compound in the form of a monoethanolamine borate.

24. The agricultural composition of any one of claims 21 to 23, further comprising an adjuvant.

25. The agricultural composition of any one of claims 21 to 24, wherein the adjuvant comprises at least one anionic surfactant, wherein the at least one anionic surfactant is selected from the group consisting of: (C)6–C18) Alkyl benzene sulfonate, calcium dodecyl benzene sulfonate, sodium alkyl benzene sulfonate, and amine (C)6–C18) Alkyl benzene sulfonate, trihydroxyethyl amine dodecyl benzene sulfonate and (C)6–C18) Alkyl ether sulfates, (C)6–C18) Alkyl ethoxylated ether sulfates (C)6–C18) Alkyl sulfate, sodium lauryl ether polyethoxylate sulfate and (C)6–C18) Alkyl phosphate, (C)6–C18) Alkoxylated sulfates, (C)6–C18) Alkoxylated phosphoric acidEsters, xylene sulfonates, cumene sulfonates, and combinations thereof.

26. The agricultural composition of claim 25, wherein the adjuvant further comprises at least one nonionic surfactant selected from the group consisting of: natural and/or synthetic (C)8–C22) Alkoxylated fatty alcohols, (C)8–C22) Ethoxylated fatty alcohols, (C)8–C22) Propoxylated fatty alcohols, (C)8–C22) Ethoxylated and propoxylated fatty alcohols, straight chain (C)4–C10) Alkyl (poly) glycosides, branched chains (C)4–C10) Alkyl (poly) glycosides; and fatty acid alkoxylated sorbitan esters, fatty acid alkoxylated sorbitol esters, fatty acid ethoxylated sorbitan esters, fatty acid ethoxylated sorbitol esters, monolaurate polyethylene glycol sorbitan esters, monopalmitoate polyethylene glycol sorbitan esters, monostearate polyethylene glycol sorbitan esters, and combinations thereof.

27. The agricultural composition of any one of claims 21 to 26, further comprising at least one additive selected from the group consisting of: preservatives, clarifiers, antifreeze agents, hydrotropes, stabilizers, antioxidants, acidulants, chelates, complexing agents, dyes, rheology modifiers, defoamers, anti-drift and water repellents, oils or other solvents, and combinations thereof.

28. The agricultural composition of any one of claims 21 to 27, further comprising at least one essential oil selected from the group consisting of: natural oils and synthetic oils, wherein the natural oils consist of terpene oils, including citrus oils.

29. The agricultural composition of any one of claims 21 to 28, further comprising water and formulated as a liquid selected from the group consisting of: solutions, concentrated solutions, dilutions, aqueous solutions, aqueous suspensions, liquid extracts, liquid creams, liquid concentrates, suspensions, concentrated suspensions, microcapsule suspensions, pastes, liquid pastes, paste concentrates, slurries, water-dispersed slurries, gels, liquid-soluble gels, and combinations thereof.

30. The agricultural composition of any one of claims 21 to 29, wherein said agricultural composition is formulated as a solid selected from the group consisting of: water dispersible powders, water soluble powders, dustable powders, floating powders, crystals, granules, water dispersible granules, water soluble granules, encapsulated granules, fine granules, microgranules, self-dispersing floating granules, capsules, microcapsules, pellets, dispersible concentrates, dry flowable, water dispersible pellets, water soluble pellets, tablets, water dispersible tablets, briquettes, flakes, and combinations thereof.

Technical Field

The present invention relates to agricultural compositions and/or adjuvants and/or tank mixes to control and/or treat and/or reverse the symptoms of diseases or defects associated with plants, particularly diseases or defects associated with vascular and other tissues of plants. In particular, the present invention relates to agricultural compositions and/or adjuvants and/or tank mixes to control and/or treat and/or reverse the symptoms of citrus greening disease (citrus greening disease) or Huanglongbing (HLB) in citrus plants. The invention also relates to a method for controlling and/or treating vascular diseases in plants.

Background

Plant pathogens prevent optimal yield production in the agricultural field and, if left uncontrolled, pose a general threat to food safety. Effective management of plant pathogens is an expensive and technically challenging task for farmers, agricultural companies, research institutes and research centers all over the world. Certain pathogens can lead to disease that cannot be effectively managed, treated, or cured, resulting in crop losses and/or the need to replace crops. Pathogens affecting plant vascular tissue are particularly important for management or control, as healthy vascular tissue is critical to the health and biological function of common plants.

The vascular bundle is part of a vascular plant transport system. Transport itself occurs in vascular tissue, which exists in two forms, xylem and phloem.

Xylem is composed of tubular molecules through which sap flows and living and structural tissues (parenchyma and fibers) that surround and support it. The tubular molecules consisting of angiosperms 'ducts and gymnosperms' tracheids and vascular plants with a higher evolutionary basis form an interwoven network of tubes of dead hollow cells connected end-to-end. Phloem is another group of ducts made up of living cells that enable the movement of solutions inside plants by means of metabolic energy. Xylem and phloem together constitute the vascular system of most land plants and evolve shortly after the plants colonize the land.

The two main functions of the vascular plant xylem hydraulic network (hydraulic network) are (i) to supply water and minerals to all tissues, and (ii) to provide mechanical support.

Vascular disease caused by bacteria often causes the bacteria to self-assemble into cell clusters and migrate with the flow of xylem sap induced by transpiration, thereby clogging the channels.

Many plant pathogenic bacterial species are present in the water conducting xylem vessels of plants where they form large aggregates of cells, biofilms, or produce plant cell degrading enzymes that block the flow of xylem sap. These activities lead to plant wilting, reduced yield, and in many cases plant death-all of which affect growers and consumers. Affected plants range from woody plants (such as grapes) to vegetables (such as tomatoes and cabbage).

It is little known how bacteria are spread and colonised in the vascular system (conize). In particular, little is known about how bacteria migrate against the direction of sap flow, which has been a difficult and important problem explaining the spread of bacteria in many plant hosts. Therefore, better control measures are constantly sought in disease management.

One very serious bacterial disease that affects and threatens citrus production worldwide is yellow dragon disease (HLB), also known as citrus greening disease, which destroys citrus crops primarily in asia, brazil, and the united states. HLB is a serious bacterial disease that affects and threatens citrus production worldwide. The causative agents of HLB have been identified as three related but distinct phloem-specific gram-negative α -proteobacteria, namely, "phloem asia" (candida Liberibacter asiaticus, CLas), "african phloem" (ca.l. africanus, CLaf) and "phloem america" (ca.l. americanus, CLam). The main vectors for the transmission of pathogens are psyllids, usually either Diaphorina citri (Diaphorina citri) or psyllid (Trioza erytreae). Further transmission may take the form of transmission of the infected substance. A three-tiered disease control scheme is proposed that includes (i) reducing inoculum (inoculum) by removing trees with HLB disease, (ii) controlling psyllid vector populations, and (iii) producing healthy trees for planting.

Basic studies of HLB are particularly difficult, as pathogenic bacteria are difficult to culture in a laboratory environment and their exact mechanism of action is therefore not clear. Pathogens are known to penetrate the phloem and attack the vascular system, clogging the phloem, preventing proper transport of water and nutrients. The function of phloem is closely related to the function of xylem and other parts of the tree. The clogging of the phloem by bacteria impedes proper juice flow, resulting in uneven nutrient spread and starch accumulation in certain leaves, thereby starving the roots of carbohydrate nutrients. This damage to the phloem occurs throughout the plant, from the root tip to the leaves and fruit. The function of xylem is closely related to that of phloem, so the entire vascular system will be affected by HLB. Due to this interconnection between xylem and phloem, any disease affecting xylem affects phloem through the same physiological association.

Huanglongbing (HLB) is the most harmful citrus-related disease and is prevalent worldwide, posing a threat to global citrus production. Typical symptoms of the disease include: yellowing of leaves, poor growth, reduced citrus fruit yield, smaller fruit, deformed fruit, lightened fruit, and plant death. There is currently no way to mitigate the effects of HLB, and the disease causes the infected plant to die within three to five years. Mottle (patch pattern) is the most important leaf symptom for diagnosis.

Disease symptoms are associated with bacterial colonization processes in the ductal tissues (phloem and xylem), resulting in the cessation or obstruction of solute transport to other parts of the plant. Once infected, as previously described, subsequent bacterial infection can obstruct the vascular system of the tree and inhibit nutrient movement. Thus, as disease progresses, effective delivery of antimicrobial agents becomes increasingly difficult.

There is currently no effective or low cost means or treatment for HLB control. In view of the rapid spread of disease and the lack of therapeutic practice, there is an urgent need for inoculants that reduce HLB (the diseased plant).

Since the pathological mechanisms of their action are poorly understood, many treatment regimens have so far focused not on controlling bacterial pathogens, but on controlling the total amount of agent. See, for example, U.S. publication No. 2010/0074972a 1.

In another U.S. patent application published as U.S. publication No. 2011/0021463, the invention seeks to target the pathogen itself with phosphonic acids, provided that the phosphonic acids inhibit the metabolic processes of oxidative phosphorylation in the pathogen. Despite efforts to develop mitigation measures, to date, no method has been effective in reversing the effects of the disease on trees, and the citrus industry worldwide is at risk unless it is successful in preventing, controlling and/or reversing the effects of HLB on trees.

European patent application No. 2988590 and U.S. publication No. 2016/0186201 disclose the production of transgenic plants that are resistant to infection by phloem-restricted microorganisms and that include induction of expression of chimeric or fusion proteins including Citrus aurantifolia (Citrus aurantifolia) phloem protein (CsPP16), connexin, and proteins with antibacterial activity. The plant genome comprises a chimeric gene encoding a fusion protein that acts as a transporter in vascular tissue of the plant.

PCT patent application published as WO 2005/079569 discloses a nanocrystalline silver composition for use in protecting plant material, in particular against microbial growth.

U.S. publication No. 2013/0266535 Al discloses insect attractants, methods for monitoring infection of citrus plants, and methods for transferring an HLB vehicle away from a predetermined citrus growth.

Stelinski et al, 2013 found that Las infected plants lack N, P, Mg, Zn and Fe, but are characterized by higher concentrations of K and B. Nwugo et al, BMC Plant Biology, 2013, described a correlation between protein expression and nutritional status of grapefruit plants before or during the onset of Las infection symptoms. Nwugo et al showed a general decrease in nutrient concentration due to Las infection, especially iron, zinc and copper, but an increase in potassium levels. Nwugo et al suggest that physiological and molecular processes associated with the response of grapefruit plants to Las infection include: a general decrease in nutrient concentration, resulting in decreased protein production associated with photosynthesis, energy production, regulation, and protein synthesis/transport; increased potassium concentration to support increased activity of starch anabolism-related protein production; increased production of peroxidase, Cu/Zn SOD and pathogen response-associated proteins.

However, there is currently no cure or effective treatment for HLB-affected trees, and any infected plants eventually die. Efforts to develop mitigation measures have not been successful in reversing the effects of disease on trees to date.

Applicants have now surprisingly found that the agricultural compositions and/or liquid agricultural adjuvants and/or tank mixes and/or processes described herein each at least ameliorate the disadvantages known in the prior art. The agricultural compositions and/or liquid agricultural adjuvants and/or tank mixes and/or methods herein can be used to control and/or treat plant diseases caused by microorganisms (including bacteria and/or fungi), viruses, and pests. Without being bound by theory, the invention described herein provides for the expansion of the vasculature of a plant vascular system, increasing sap mobility, thereby improving nutrient and/or pharmaceutical compound and/or beneficial compound absorption, providing an improved level of photosynthesis. Additionally or alternatively, the invention described herein may promote the degradation of foreign plugs by microorganisms (including bacteria and/or fungi), viruses, or pests within the vascular system of a plant, increasing sap mobility, thereby improving nutrient and/or medicinal compound and/or beneficial compound absorption, providing improved levels of photosynthesis.

Disclosure of Invention

The present invention provides agricultural compositions and/or liquid agricultural adjuvants and/or tank mixes and/or methods for improving plant health and maintaining control of phytopathogenic bacteria and/or endophytes in plants. For example, the present invention provides methods of ameliorating citrus greening disease or yellowshoot (HLB) caused by the pathogenic bacterium, the genus phlobacterium, in citrus plants. The agricultural composition and/or liquid agricultural adjuvant may comprise tannic acid. The agricultural composition may be provided in solid, liquid, gel or other form. When used, the agricultural composition and/or adjuvant promotes vascular dilation of plant tissue, resulting in restoration and/or improvement and/or increase in the level of photosynthesis, and/or improving plant health, resulting in improvement of HLB symptoms.

Surprisingly, applying the agricultural composition and/or liquid agricultural adjuvant and/or tank mix described herein to citrus trees with HLB restores the water balance in the trees by allowing xylem vascular bundles, which are the main upward transport route for water, to restore their function. The new leaves are in healthy green color. This results in a return of photosynthesis to normal levels. This restoration of HLB-affected trees is surprising because previous efforts to apply modifiers (e.g., macro and micro nutrients) have eventually failed.

Without being bound by theory, applicants also believe that the expansion of the vascular tissue also promotes more efficient delivery of the antiseptic to the bacterial pathogen itself and may allow it to be effectively eradicated. Additionally or alternatively, the invention described herein may promote the degradation of foreign plugs by microorganisms (including bacteria and/or fungi), viruses, or pests within the vascular system of a plant, increasing sap mobility, thereby improving nutrient and/or medicinal compound and/or beneficial compound absorption, providing improved levels of photosynthesis.

The present invention provides an improved agricultural composition and/or adjuvant and/or tank mix and/or method of expanding vascular tissue in plants for treating and/or containing (continain) and/or controlling and/or reversing the symptoms of diseases or defects associated with vascular and other plant tissues.

Broadly, the present invention provides the use of tannic acid for the treatment and/or control of vascular disease in plants, preferably citrus greening disease or Huanglongbing (HLB) of citrus plants.

Tannic acid can be a specific form of tannin, a polyphenol, which can be synthetic or naturally produced by extraction with water or an organic solvent, and can be produced by (but is not limited to) at least one of the following groups: tara pods (Tara pod) (Caesalpinia spinosa), gallnut (Gallnuts) (Rhus semialata or gallnut (Quercus infetoria)), Chinese Sumac leaves (sician Sumac leaves) (coriaria sinica), turkey or Chinese gallnut nutgall (Rhus species)), Chinese chestnut trees (European chestnuts) (Castanea sativa), American chestnut trees (American chestnuts) (Quercus nigra), American chestnut trees (American chestnuts), and Acacia trees (Acacia specas).

Tannic acid can be formulated as, but not limited to, at least one of the following groups: solids, liquids and gels.

The tannic acid can also include other chemicals to provide agricultural compositions.

Tannic acid or agricultural compositions comprising tannic acid can be provided in concentrated or diluted form. The composition may be stable.

According to a first aspect of the present invention there is provided an agricultural composition for the control and/or treatment of citrus greening disease or Huanglongbing (HLB), said agricultural composition comprising tannic acid. The composition may generally be stable.

Tannic acid can be a specific form of tannin, a polyphenol, which can be synthetic or naturally produced by extraction with water or an organic solvent, and can be produced by (but is not limited to) at least one of the following groups: tara pods (Tara pod) (Caesalpinia spinosa), gallnut (Gallnuts) (Rhus semialata or gallnut (Quercus infetoria)), Chinese Sumac leaves (sician Sumac leaves) (coriaria sinica), turkey or Chinese gallnut nutgall (Rhus species)), Chinese chestnut trees (European chestnuts) (Castanea sativa), American chestnut trees (American chestnuts) (Quercus nigra), American chestnut trees (American chestnuts), and Acacia trees (Acacia specas).

The agricultural composition may also include nutrient compounds provided as fertilizer components. Fertilizer components may include, but are not limited to, the following groups: nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), boron (B), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silicon (Si) or zinc (Zn), wherein the soluble or insoluble source of nutrients may be ammonium salts, nitrates, chlorides, carbonates, phosphates, phosphites, sulfates, molybdates, acetates, citrates, formates, borates, thiosulfates, silicates or acids, amides, amines, hydroxides, oxides. It is to be understood that various other nutrient compounds are contemplated. In certain embodiments, the fertilizer component may be monoethanolamine borate.

The agricultural composition may further comprise an adjuvant.

The agricultural composition may further comprise a surfactant. The surfactant may be at least one anionic surfactant and/or at least one nonionic surfactant and/or anionic and nonionic surfactants.

The at least one anionic surfactant may be selected from, but is not limited to, the following group: (C)6–C18) Alkyl benzene sulfonate, calcium dodecyl benzene sulfonate, sodium alkyl benzene sulfonate, and amine (C)6–C18) Alkyl benzene sulfonate, trihydroxyethyl amine dodecyl benzene sulfonate and (C)6–C18) Alkyl ether sulfates, (C)6–C18) Alkyl ethoxylated ether sulfates (C)6–C18) Alkyl sulfate, sodium lauryl ether polyethoxylate sulfate and (C)6–C18) Alkyl phosphate, (C)6–C18) Alkoxylated sulfates, (C)6–C18) Alkoxylated phosphate esters, xylene sulfonates, cumene sulfonates, and combinations thereof.

The at least one nonionic surfactant may be selected from, but is not limited to, the following group: natural and/or synthetic (C)8–C22) Alkoxylated fatty alcohols, (C)8–C22) Ethoxylated fatty alcohols, (C)8–C22) Propoxylated fatty alcohols, (C)8–C22) Ethoxylated and propoxylated fatty alcohols, straight chain (C)4–C10) Alkyl (poly) glycosides, branched chains (C)4–C10) Alkyl (poly) glycosides; and fatty acid alkoxylated sorbitan esters, fatty acid alkoxylated behenatesSorbitol esters, fatty acid ethoxylated sorbitan esters, fatty acid ethoxylated sorbitol esters, monolaurate polyethylene glycol sorbitan esters, monopalmitate polyethylene glycol sorbitan esters, monostearate polyethylene glycol sorbitan esters, and combinations thereof.

The ethoxylated fatty alcohol of the fatty acid may have a degree of ethoxylation of from 1 to 50, more preferably from 2 to 30, most preferably from 3 to 10.

Some alkoxylated alcohols contemplated for use include those based on branched alcohols, e.g., Guerbet alcohol, e.g., 2-propylheptanol and 2-ethylhexanol, and C10-OXO-alcohol or C13-OXO-alcohols, i.e. whose main constituent consists of at least one branched C10Alcohol or C13Alcohol mixtures formed from alcohols, as well as alcohols purchased from Exxon Mobile Chemicals as Exxal alcohol (Exxal alcohol) and alcohols purchased from Shell Chemical as nordol alcohol (Neodol alcohol).

The agricultural composition may further comprise an additive. The additive may be, but is not limited to, at least one of the following groups: preservatives, clarifiers, antifreeze agents, hydrotropes, stabilizers, antioxidants, acidulants, chelates, complexing agents, dyes, rheology modifiers, defoamers, anti-drift and water repellents, oils or other solvents, and combinations thereof.

The agricultural composition further comprises at least one essential oil. The at least one essential oil may be a natural compound, such as a citrus oil, a component of a citrus oil, a terpene oil, wherein the terpene oil comprises d-limonene or one or more terpene containing natural oils, wherein the one or more terpene containing natural oils comprise at least 50% terpenes, wherein the essential oil is selected from the group consisting of: orange oil, grapefruit oil, lemon oil (lemon oil), lime oil (lime oil), tangerine oil (orange oil), mocott citrus oil (murcot citrus oil), citronella oil, other citrus oils, or combinations thereof.

The agricultural composition may further comprise water.

The agricultural composition may further comprise, but is not limited to, biocides from the following group: bactericides, fungicides, herbicides, insecticides, acaricides, ovicides, insecticides, nematicides and combinations thereof.

The agricultural composition may also be provided as a liquid. Additionally and/or alternatively, the agricultural composition may be provided as a solid, which may preferably be provided as a powder. Applicants contemplate various formulation types, including but not limited to: a) solid: a powder, a water-dispersible powder, a water-soluble powder, a dustable powder, a floating powder (flo-dust), a crystal, a granule, a water-dispersible granule, a water-soluble granule, an encapsulated granule, a fine granule, a microgranule, a self-dispersing floating granule, a capsule, a microcapsule, a pellet, a dispersible concentrate, a dry flowable, a water-dispersible pellet, a water-soluble pellet, a tablet, a water-dispersible tablet, a briquette, a flake, and combinations thereof; b) liquid: solutions, concentrated solutions, aqueous suspensions, liquid extracts, liquid creams, liquid concentrates, suspensions, concentrated suspensions, microcapsule suspensions, and combinations thereof; c) fluid: pastes, liquid pastes, paste concentrates, slurries, water-dispersed slurries, gels, liquid-soluble gels, and combinations thereof.

The agricultural composition may be provided in a concentrated form and/or in a diluted form. The concentrated agricultural composition may be diluted prior to use in the method, and the diluent may preferably be water. It should be understood that various other and/or alternative chemicals are contemplated as diluents.

When used in the process, the agricultural composition (in concentrated or diluted form) may be added to the tank mix at a rate of from about 0.01 to about 5.0 kg/ha or from about 0.01 to about 5.0 liters/ha. The applicant has envisaged various tank mix ratios (tank mix ratios).

In one embodiment of the present invention, an agricultural composition comprises: tannic acid in dry concentrated or diluted form, 0.01% to 1.0% as a pot mix or added to a fertilizer composition containing 0.1% to 50.0% relative tannic acid; wherein the fertilizer component contains from 0.1% to 80.0% of one or more relative nutrients and the fertilizer may comprise a source of: nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), boron (B), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silicon (Si), or zinc (Zn); and wherein the agricultural composition may be added to the tank mix at a rate of 0.1 to 20.0 kg/ha or 0.1 to 20.0 liters/ha, applied in the tank mix with other chemicals for the treatment of plant vascular disease; or wherein tannic acid in concentrated or diluted form is added to the tank mix at a rate of 0.01 to 5.0 kg/ha or 0.01 to 5.0 l/ha, applied in the tank mix with one or more nutrients and other chemicals for the treatment of vascular diseases. Agricultural compositions may be used for biocidal, bactericidal, insecticidal and/or fungicidal applications.

According to a second aspect of the present invention, there is provided a liquid agricultural adjuvant for the control and/or treatment of citrus greening disease or Huanglongbing (HLB), the liquid agricultural adjuvant comprising:

at least one essential oil, preferably a terpene;

at least one anionic surfactant;

at least one nonionic surfactant; and

tannic acid.

The liquid agricultural adjuvant has from about 0.1% to about 20% by weight of a terpene, from about 0.1% to about 25% by weight of tannic acid, the at least one anionic surfactant is present in an amount from about 1% to about 50% by weight, and the at least one nonionic surfactant is present in an amount from about 1% to about 50% by weight, wherein the liquid agricultural adjuvant is provided in a concentrated form.

Liquid agricultural adjuvants may also comprise nutrient compounds provided as fertilizer components. Fertilizer components may include, but are not limited to, the following groups: nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), boron (B), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silicon (Si) or zinc (Zn), wherein the soluble or insoluble source of nutrients may be ammonium salts, nitrates, chlorides, carbonates, phosphates, phosphites, sulfates, molybdates, acetates, citrates, formates, borates, thiosulfates, silicates or acids, amides, amines, hydroxides, oxides. It is to be understood that various other nutrient compounds are contemplated. In certain embodiments, the fertilizer component may be monoethanolamine borate.

In certain embodiments of the invention, the fertilizer component comprises from about 0.1% to about 80.0% of one or more relative nutrients.

Liquid agricultural adjuvants (in concentrated form) can be diluted with water or other solvents to provide a diluted form. In use, the concentrated and/or diluted form may be mixed with other chemicals and/or fertiliser components and/or plant protection products (including pesticides and/or fungicides).

Tannic acid can be a specific form of tannin, a polyphenol, which can be synthetic or naturally produced by extraction with water or an organic solvent, and can be produced by (but is not limited to) at least one of the following groups: tara pods (Tara pod) (Caesalpinia spinosa), gallnut (Gallnuts) (Rhus semialata or gallnut (Quercus infetoria)), Chinese Sumac leaves (sician Sumac leaves) (coriaria sinica), turkey or Chinese gallnut nutgall (Rhus species)), Chinese chestnut trees (European chestnuts) (Castanea sativa), American chestnut trees (American chestnuts) (Quercus nigra), American chestnut trees (American chestnuts), and Acacia trees (Acacia specas). In certain embodiments of the second aspect, tannic acid can be added to the tank mix at a rate of from about 0.01 to about 20.0 kilograms per hectare or from about 0.1 to about 20.0 liters per hectare.

The at least one essential oil may be a natural compound, such as a citrus oil, a component of a citrus oil, a terpene oil, wherein the terpene oil comprises d-limonene or one or more terpene containing natural oils, wherein the one or more terpene containing natural oils comprise at least 50% terpenes, wherein the essential oil is selected from the group consisting of: orange oil, grapefruit oil, lemon oil (lemon oil), lime oil (lime oil), tangerine oil (orange oil), mocott citrus oil (murcot citrus oil), citronella oil, other citrus oils, or combinations thereof.

The at least one anionic surfactant may be selected from, but is not limited to, the following group: (C)6–C18) Alkyl benzene sulfonate, calcium dodecyl benzene sulfonate, sodium alkyl benzene sulfonate, and amine (C)6–C18) Alkyl benzene sulfonate, trihydroxyethyl amine dodecyl benzene sulfonate and (C)6–C18) Alkyl ether sulfates, (C)6–C18) Alkyl ethoxylated ether sulfates (C)6–C18) Alkyl sulfate, sodium lauryl ether polyethoxylate sulfate and (C)6–C18) Alkyl phosphate, (C)6–C18) Alkoxylated sulfates, (C)6–C18) Alkoxylated phosphate esters, xylene sulfonates, cumene sulfonates, and combinations thereof.

The at least one nonionic surfactant may be selected from, but is not limited to, the following group: natural and/or synthetic (C)8–C22) Alkoxylated fatty alcohols, (C)8–C22) Ethoxylated fatty alcohols, (C)8–C22) Propoxylated fatty alcohols, (C)8–C22) Ethoxylated and propoxylated fatty alcohols, straight chain (C)4–C10) Alkyl (poly) glycosides, branched chains (C)4–C10) Alkyl (poly) glycosides; and fatty acid alkoxylated sorbitan esters, fatty acid alkoxylated sorbitol esters, fatty acid ethoxylated sorbitan esters, fatty acid ethoxylated sorbitol esters, monolaurate polyethylene glycol sorbitan esters, monopalmitoate polyethylene glycol sorbitan esters, monostearate polyethylene glycol sorbitan esters, and combinations thereof.

The ethoxylated fatty alcohol of the fatty acid may have a degree of ethoxylation of from 1 to 50, more preferably from 2 to 30, most preferably from 3 to 10.

Some alkoxylated alcohols contemplated for use include those based on branched alcohols, e.g., Guerbet alcohol, e.g., 2-propylheptanol and 2-ethylhexanol, and C10-OXO alcohol or C13OXO alcohols, i.e. containing as its main constituent at least one branchChain C10Alcohol or C13Alcohol mixtures formed from alcohols, as well as alcohols purchased from Exxon Mobile Chemicals as Exxal alcohol (Exxal alcohol) and alcohols purchased from Shell Chemical as nordol alcohol (Neodol alcohol).

The liquid agricultural adjuvant may further comprise an additive, which is, but not limited to, selected from the group consisting of: preservatives, clarifiers, antifreeze agents, hydrotropes, stabilizers, antioxidants, acidulants, chelates, complexing agents, dyes, rheology modifiers, defoamers, anti-drift and water repellents, oils or other solvents, and combinations thereof.

In certain embodiments of the present invention, the at least one essential oil may be present in an amount of from about 0.1% to about 20% by weight, the tannic acid may be present in an amount of from about 0.1% to about 25% by weight, the at least one anionic surfactant may be present in an amount of from about 1% to about 50% by weight, and the at least one nonionic surfactant may be present in an amount of from about 1% to about 50% by weight. This embodiment may provide a liquid agricultural adjuvant in a concentrated form. It is understood that liquid agricultural adjuvants may also be diluted with water or other solvents.

In other embodiments of the present invention, the at least one essential oil may be present in an amount of from about 0.1% to about 15%, preferably from about 2% to about 10%, the tannic acid may be present in an amount of from about 0.1% to about 20%, preferably from about 3% to about 10%, the at least one anionic surfactant may be present in an amount of from about 3% to about 20%, and the at least one nonionic surfactant may be present in an amount of from about 5% to about 30%. This embodiment may provide a liquid agricultural adjuvant in a concentrated form. It is understood that liquid agricultural adjuvants may also be diluted with water or other solvents.

The liquid agricultural adjuvant may also comprise water and other additives, typically such that the liquid agricultural adjuvant may comprise from about 0.1% to about 20% by weight of at least one essential oil of high terpene content; about 0.1 wt% to about 25 wt% tannic acid; from about 1% to about 50% by weight of at least one anionic surfactant; from about 1% to about 50% by weight of at least one nonionic surfactant; and from about 2% to about 80% by weight of water and/or other additives. This embodiment can still provide a liquid agricultural adjuvant in a concentrated form.

In an exemplary embodiment of the invention, there is provided a liquid agricultural adjuvant comprising at least one essential oil (typically high terpene content) present in an amount of from about 0.1% to about 20% by weight, preferably from about 2% to about 10% by weight; tannic acid present in an amount of about 0.1 to about 25 weight percent, preferably about 3 to about 10 weight percent; at least one anionic surfactant present in an amount of about 3% to about 20% by weight; and at least one nonionic surfactant present in an amount of from about 5% to about 30% by weight; and is

Wherein the at least one essential oil with high terpene content (at least one essential oil high terpene content) may be a natural compound, e.g. an essential oil, a citrus oil, a component of a citrus oil, a terpene oil, wherein the terpene oil comprises d-limonene or one or more natural terpene containing oils, wherein the one or more natural terpene containing oils comprise at least 50% terpenes, wherein the essential oil is selected from the group consisting of: orange oil, grapefruit oil, lemon oil (lemon oil), lime oil (lime oil), tangerine oil (orange oil), mocott citrus oil (murcot citrus oil), citronella oil, other citrus oils, or combinations thereof; and is

Wherein the at least one anionic surfactant may be selected from, but not limited to, the following group: (C)6–C18) Alkyl benzene sulfonate, calcium dodecyl benzene sulfonate, sodium alkyl benzene sulfonate, and amine (C)6–C18) Alkyl benzene sulfonate, trihydroxyethyl amine dodecyl benzene sulfonate and (C)6–C18) Alkyl ether sulfates, (C)6–C18) Alkyl ethoxylated ether sulfates (C)6–C18) Alkyl sulfate, sodium lauryl ether polyethoxylate sulfate and (C)6–C18) Alkyl phosphate, (C)6–C18) Alkoxylated sulfates, (C)6–C18) Alkoxylated phosphate esters, xylene sulfonates, cumene sulfonates, and combinations thereof; and is

Wherein the at least one non-ionic surfactant may be selected from, but is not limited to, the group of: (C)8–C22) Alkoxylated fatty alcohols, (C)8–C22) Ethoxylated fatty alcohols, (C)8–C22) Propoxylated fatty alcohols, (C)8–C22) Ethoxylated and propoxylated fatty alcohols, straight chain (C)4–C10) Alkyl (poly) glycosides, branched chains (C)4–C10) Alkyl (poly) glycosides; and fatty acid alkoxylated sorbitan esters, fatty acid alkoxylated sorbitol esters, fatty acid ethoxylated sorbitan esters, fatty acid ethoxylated sorbitol esters, monolaurate polyethylene glycol sorbitan esters, monopalmitoate polyethylene glycol sorbitan esters, monostearate polyethylene glycol sorbitan esters, and combinations thereof.

Exemplary embodiments of the present disclosure may include water and/or other additives as diluents, wherein the liquid agricultural adjuvant may include from about 0.1% to about 20% by weight of at least one essential oil of high terpene content; about 0.1 wt% to about 25 wt% tannic acid; from about 1% to about 50% by weight of at least one anionic surfactant; and about 1% to about 50% by weight of at least one nonionic surfactant; and from about 2% to about 80% by weight of water and/or other additives. This embodiment can still provide a liquid agricultural adjuvant in a concentrated form.

The additive may be, but is not limited to, at least one of the following groups: preservatives, clarifiers, antifreeze agents, hydrotropes, stabilizers, antioxidants, acidulants, chelates, complexing agents, dyes, rheology modifiers, defoamers, anti-drift and water repellents, oils or other solvents, and combinations thereof.

The oils may be natural compounds modified by esterification or transesterification, for example, alkyl fatty acid esters, such as methyl, ethyl, propyl, butyl, 2-ethylhexyl, or dodecyl esters,and preferably a diol or glycerol fatty acid, e.g. (C)10–C22) Fatty acid esters, such as those from vegetable oils, preferably those from oleaginous plant species, such as soybean, corn, sunflower, rapeseed oil (rapeseed oil), cottonseed oil, linseed oil, palm oil, safflower, coconut oil, castor oil, olive oil, canola oil (canola oil), and the like, either pure or mixed with essential or edible oils extracted from various plants or plant parts, such as trees (trees), shrubs (shrubs), leaves, flowers, grasses, fluids, herbs, fruits, and seeds, or mixed with each other, in combination with one or more oils.

In other embodiments, the oil may be a natural compound, such as an essential oil, a citrus oil, a component of a citrus oil, a terpene oil, wherein the terpene oil comprises d-limonene or one or more terpene-containing natural oils, wherein the one or more terpene-containing natural oils comprise at least 50% terpenes selected from the group consisting of: orange oil, grapefruit oil, lemon oil (lemon oil), lime oil (lime oil), tangerine oil (orange oil), mocott citrus oil (murcot citrus oil), citronella oil, other citrus oils, or combinations thereof.

The liquid agricultural adjuvant (in concentrated form) may contain 0.1 to 25% by weight tannic acid, wherein the liquid agricultural adjuvant (in concentrated form) may be an emulsifiable and/or microemulsifiable liquid adjuvant that can be diluted in a ratio of 1:5000 to 1:10 by air-assisted sprayers, conventional sprayers, ultra-low capacity devices (such as pneumatic, electrostatic humidifiers and spray devices) and chemical systems (such as rotary sprayers) to provide a diluted liquid agricultural adjuvant for use in tank mixes or irrigation systems mixed with fertilizer nutrients, water or other chemicals. The liquid agricultural adjuvant used may provide biocidal properties.

Liquid agricultural adjuvants may also include, but are not limited to, biocides of the following group: bactericides, fungicides, herbicides, insecticides, acaricides, ovicides, insecticides, nematicides and combinations thereof.

According to a third aspect of the present invention there is provided a tank mix for application to plants to control and/or treat vascular diseases, the tank mix comprising the agricultural composition of the first aspect and/or the liquid agricultural adjuvant of the second aspect added to an aqueous tank mix. The tank mixture may preferably be stable.

The tank mix may also include, but is not limited to, biocides from the following group: bactericides, fungicides, herbicides, insecticides, acaricides, ovicides, insecticides, nematicides and combinations thereof.

The tank mix may include an agricultural composition and/or adjuvant comprising about 0.1 wt% to about 25 wt% tannic acid.

The tank mixture may also include a fertilizer component, for example, a solution of monoethanolamine borate, which contains about 0.1% to about 15.0% relative boron.

The tank mix may also contain fungicides and/or fertilizers of the type based on elemental sulphur suspension concentrates, which contain from 10.0% to 70.0% relative sulphur.

The tank mix may also include a germicidal composition in the form of a copper oxychloride suspension concentrate that contains from 10.0% to 40.0% relative copper. The tank mix may also include other chemicals.

When used, a preferred embodiment of the pot mix is formulated such that when applied to plants, tannic acid is applied at an amount of 0.1 to 1.5 liters per hectare; and/or monoethanolamine borate is applied at a rate of 1.0 to 5.0 liters per hectare; and/or the concentrated suspension of elemental sulphur is applied at an amount of from 1.0 to 4.0 litres per hectare; and/or the copper concentrate suspension is applied at an amount of 0.5 to 2.0 liters per hectare; and/or wherein the pot mix is applied to the plant at least once, but preferably 6 (six) times, within a season.

It is to be understood that the tank mixture may contain several other chemicals without departing from the scope or spirit of the present invention.

According to a fourth aspect of the present invention there is provided a method of controlling and/or treating vascular disease (preferably citrus greening disease or HLB) in a plant, said method comprising the steps of: tannic acid is applied to a plant in need of tannic acid, either alone or as part of a formulation.

Tannic acid can be a specific form of tannin, a polyphenol, which can be synthetic or naturally produced by extraction with water or an organic solvent, and can be produced by (but is not limited to) at least one of the following groups: tara pods (Tara pod) (Caesalpinia spinosa), gallnut (Gallnuts) (Rhus semialata or gallnut (Quercus infetoria)), Chinese Sumac leaves (sician Sumac leaves) (coriaria sinica), turkey or Chinese gallnut nutgall (Rhus species)), Chinese chestnut trees (European chestnuts) (Castanea sativa), American chestnut trees (American chestnuts) (Quercus nigra), American chestnut trees (American chestnuts), and Acacia trees (Acacia specas).

In use, the method provides for expansion of the vascular system and thereby treat and/or control disease, particularly citrus greening disease or HLB. In use, the method also facilitates the unclogging of bacterial colonies from plant vascular tissue and thereby the treatment and/or control of diseases, especially citrus greening disease or HLB.

The method may comprise the steps of: applying the agricultural composition of the first aspect of the invention and/or applying the liquid agricultural adjuvant of the second aspect of the invention and/or applying the tank mix of the third aspect of the invention to a plant in need thereof, in which citrus greening disease or HLB is controlled and/or treated.

There is further provided an agricultural plant of the first aspect; a liquid agricultural adjuvant of the second aspect; the tank mixture of the third aspect; and/or the method of the fourth aspect, substantially as described herein, with reference to and/or as illustrated in any one or more of the figures and/or examples herein.

The applicant has surprisingly found that the above and following aspects according to the present invention at least improve the symptoms of vascular disease in plants, in particular citrus greening disease or HLB in citrus trees. Without being bound by theory, the invention described herein provides for the expansion of the vasculature of a plant vascular system, increases sap fluidity, thereby improving nutrient and/or anti-pathogenic compounds and/or beneficial compounds uptake, provides for improved levels of photosynthesis, and/or improves plant health, thereby improving HLB symptoms. It is also believed that increased vascular dilation provides a more effective method of delivering a biocide to plant vascular tissue, the biocide being selected from, but not limited to, the group consisting of: bactericides, fungicides, herbicides, insecticides, acaricides, ovicides, insecticides, nematicides and combinations thereof. Additionally or alternatively, the invention described herein may promote the degradation of foreign plugs by microorganisms (including bacteria and/or fungi), viruses or pests within the vascular system of a plant, increasing sap mobility, thereby improving the absorption of nutrients and/or medicinal compounds and/or beneficial compounds and/or plant protection products, providing improved levels of photosynthesis.

Brief description of the drawings

These photographs were taken from the central plants of each treatment plot in exactly the same position, using permanently fixed support stakes for each tree in the trial, and at the same height to achieve similar angles. The method was used throughout the experiment for at least 3 years.

FIG. 1: the pictures from experiment # 1-treatment #1 witness untreated citrus trees-compare day 0 after 12 days 4 and 5 days 10 and 2018 (d.a.t.) in 2017.

FIG. 2: the pictures from experiment # 1-treatment #7 demonstrated treated citrus trees-comparing day 0 at 12 days 4-2017 and day 189 (d.a.t.) after treatment at 5 days 10-2018.

FIG. 3: the pictures from experiment # 1-treatment #8 demonstrated treated citrus trees-comparing day 0 at 12 days 4-2017 and day 189 (d.a.t.) after treatment at 5 days 10-2018.

FIG. 4: the pictures from experiment # 1-treatment #9 demonstrate treated citrus trees-compare day 0 after 12 days 4-2017 and day 189 after 5 days 10-2018 (d.a.t.). FIG. 5: the pictures from experiment # 1-treatment #10 demonstrated treated citrus trees-comparing day 0 at 12 days 4-2017 and day 189 (d.a.t.) after treatment at 5 days 10-2018.

FIG. 6 is a diagram of: pictures from experiment # 2-treatment #1, which witnessed untreated citrus trees-compare day 0 after treatment on day 05, 10/2017 and day 116 (d.a.t.) after treatment on day 29, 1/2018.

FIG. 7: pictures from experiment # 2-treatment #11 treated citrus trees-compare day 0 after 10/05 of 2017 and day 116 after 1/29 of 2018 (d.a.t.).

FIG. 8: pictures from experiment # 2-treatment #12 treated citrus trees-compare day 0 after 10/05 of 2017 and day 116 after 1/29 of 2018 (d.a.t.).

FIG. 9: pictures from experiment # 2-treatment #13 treated citrus trees-compare day 0 after 10/05 of 2017 and day 116 after 1/29 of 2018 (d.a.t.).

FIG. 10: an electron micrograph taken through citrus tree foliage wherein (a) shows a cross-section of an untreated citrus plant having HLB, and (b) shows a cross-section of a citrus plant having HLB treated with an agricultural composition of the invention. (a) Showing bacterial blockage in the vascular system and (b) showing improvement in bacterial blockage in the vascular system after application of the present invention.

Detailed Description

To avoid repetition, the summary is repeated herein by reference. Generally, tannic acid is provided for controlling and/or treating vascular diseases in plants. In a first aspect of the invention, there is provided an agricultural composition as described above. In a second aspect of the invention, there is provided a stable liquid agricultural adjuvant as described above. In a third aspect of the invention, a tank mixture is provided comprising the first and second aspects. A fourth aspect is provided as a method of controlling and/or treating vascular disease in plants, preferably citrus greening disease or HLB.

In certain embodiments of the second invention, stable liquid agricultural adjuvants are provided comprising at least one high terpene content essential oil (essential high terpene content), at least one anionic surfactant, at least one nonionic surfactant, and tannic acid. The liquid agricultural adjuvant may be further diluted with water or other solvents and then mixed with fertilizer components and/or other chemicals. Liquid agricultural adjuvants containing tannic acid can be added to tank mixes at a rate of 0.1 to 20.0 kg/ha or 0.1 to 20.0 liters/ha to treat vascular disease in plants, alone or in combination with other chemicals.

The above treatments by applying agricultural compositions on plants and/or by applying stable liquid agricultural adjuvants and/or by using tank mixes have shown a very severe deterioration of trees already able to contain (continain) and/or control and/or reverse the effects of HLB and other diseases that endanger the vascular bundle by a series of foliar sprays. The above treatment enables the growth of shoots, roots and fruits to be vigorous.

The present disclosure relates to methods of making agricultural compositions and/or liquid agricultural adjuvants and/or tank mixes generally in the agricultural field and methods of use. Applicants have now surprisingly found that the agricultural compositions and/or liquid agricultural adjuvants and/or tank mixes and/or processes described herein at least ameliorate the disadvantages known in the prior art. Without being bound by theory, the invention described herein provides for the expansion of the vasculature of a plant vascular system, increasing sap mobility, thereby improving nutrient and/or anti-pathogenic compound and/or beneficial compound uptake, providing for improved levels of photosynthesis. Expansion of vascular tissue may also provide for more efficient delivery of biocides to the diseased areas of the plant. In addition, citrus plants with citrus greening disease or HLB show clear signs of health improvement. Additionally or alternatively, the invention described herein may promote the degradation of foreign plugs by microorganisms (including bacteria and/or fungi), viruses or pests within the vascular system of a plant, increasing sap mobility, thereby improving the absorption of nutrients and/or medicinal compounds and/or beneficial compounds and/or plant protection products, providing improved levels of photosynthesis.

Definition of

The term "adjuvant" as used herein is a broad term having its ordinary and customary meaning to those of ordinary skill in the art (and is not limited to a specific or customized meaning), and refers to, but is not limited to, agents that modify the effect of other agents, and more specifically, to enhance the efficacy of pesticides (e.g., herbicides, insecticides, fungicides, plant protection products, and other agents).

The term "stable" as used herein is a broad term, combined with or otherwise associated with the term "formulation" and will be given its ordinary and customary meaning to those of ordinary skill in the art (and is not limited to a special or customized meaning) and refers to, but is not limited to, formulation stability, that is, the ability of a formulation to resist changes in its properties over time, and more specifically, its inherent characteristics do not change significantly over time during the time that the product remains on the market for sale to the end customer, and thus, is given its ordinary meaning as is customary to those of ordinary skill in the art.

The term "alcohol" as used herein is a broad term that will be given its ordinary and customary meaning to those of ordinary skill in the art (without being limited to a specific or customized meaning) and refers to, without limitation, any of the compounds described herein that contain one or more hydroxyl groups, or any compound that is substituted or functionalized with one or more hydroxyl groups to contain one or more hydroxyl groups.

The term "ester" as used herein is a broad term that will impart its ordinary and customary meaning to those of ordinary skill in the art (without being limited to a specific or customized meaning) and refers to, without limitation, any compound described herein that contains one or more ester groups, or that is substituted or functionalized with one or more ester groups to contain one or more ester groups. Esters include, but are not limited to, fatty acid esters.

The term "glycol" as used herein is a broad term that will be given its ordinary and customary meaning to those of ordinary skill in the art (without limitation to a special or customized meaning) and may include glycols (diols), such as polyalkylene glycols, such as polyethylene glycol (having the formula H (OCH)2CH2)nPolymers of OH, where n is greater than 3), polypropylene glycol, or glycols containing monomers comprising longer hydrocarbon chains.

The term "terpene" as used herein is a broad term having its ordinary and customary meaning to those of ordinary skill in the art (without limitation to a special or customized meaning) and refers to, without limitation, any compound extracted from the resin of a plant (e.g., conifer) or a synthetic compound having the same structure as a plant-derived terpene. The terpenes compriseHydrocarbons and terpenoids containing additional functional groups and essential oils. The terpene may comprise a compound having the formula (C)5H8)nWherein n is the number of linked isoprene units (e.g., 1, 2,3, 4, 5, 6, 7, 8, 9, 10 or more).

The term "terpene-containing natural oil" as used herein is a broad term that will be given its ordinary and customary meaning to those of ordinary skill in the art (without limitation to a special or customized meaning) and refers to, but is not limited to, natural oils containing at least 50% terpene selected from (but not limited to) the group consisting of: orange oil, grapefruit oil, lemon oil (lemon oil), lime oil (lime oil), tangerine oil (orange oil), citronella oil, and pine oil or components thereof.

As used herein, the term "sulfoxide" is a broad term that is to be given its ordinary and customary meaning to those of ordinary skill in the art (without limitation to a special or customized meaning), and refers to, but is not limited to, any compound described herein that contains one or more sulfinyl groups (SO), or is substituted with one or more sulfinyl groups or is functionalized to contain one or more sulfinyl groups.

When a group is described as "optionally substituted," the group may be unsubstituted or substituted with one or more of the indicated substituents. Likewise, when a group is described as "unsubstituted or substituted," if substituted, the substituent may be selected from one or more of the substituents shown. If no substituent is specified, it is intended that the specified "optionally substituted" or "substituted" group may be substituted with one or more groups individually and independently selected from the group consisting of: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, heteroaralkyl, (heteroalicyclyl) alkyl, hydroxy, protected hydroxy, alkoxy, aryloxy, acyl, mercapto, alkylthio, arylthio, cyano, halogen, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, protected C-carboxy, O-carboxy, isocyanato, thiocyanato, isothiocyanato, nitro, silyl, thionoyl (sulfenyl), sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethylsulfonyl, Trihalomethylsulfonylamino (trihalomethaneesulfonamido), amino, mono-and di-substituted amino, and protected derivatives thereof.

As used herein, the term "alkyl" is a broad term that will be given its ordinary and customary meaning to those of ordinary skill in the art (without being limited to a specific or customized meaning) and refers to, but is not limited to, straight or branched, acyclic or cyclic, unsaturated or saturated aliphatic hydrocarbons containing 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36 or more carbon atoms, while the term "lower alkyl" refers to an alkyl group containing 1, 2,3, 4, 5 or 6 carbon atoms. Representative saturated straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and the like; and saturated branched alkyl groups include isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, and the like. Unsaturated alkyl groups contain at least one double or triple bond between adjacent carbon atoms (referred to as "alkenyl" or "alkynyl", respectively). Representative straight and branched chain alkenyls include ethenyl, propenyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2, 3-dimethyl-2-butenyl, and the like; and representative straight and branched alkynyl groups include ethynyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 3-methyl-1-butynyl, and the like. Typical alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hentriacontyl, dotriacontyl, tritriacontyl, tetratriacontyl, pentacosyl, and hexacosyl. Alkyl groups may be substituted or unsubstituted.

As used herein, the term "alkoxy" is a broad term that will convey its ordinary and customary meaning to those skilled in the art (without limitation to a special or customized meaning), and refers to, but is not limited to, an alkyl moiety (i.e., -O-alkyl) attached through an oxygen bridge, e.g., methoxy, ethoxy, and the like.

As used herein, the term "thioalkyl" is a broad term that will convey its ordinary and customary meaning to those skilled in the art (without limitation to a special or customized meaning), and refers to, but is not limited to, an alkyl moiety (i.e., -S-alkyl) attached through a sulfur bridge, such as methylthio, ethylthio, and the like.

As used herein, the term "hydrocarbon" is a broad term that will be given its ordinary and customary meaning to those of ordinary skill in the art (without limitation to a special or customized meaning), and refers to, but is not limited to, any compound containing only carbon and hydrogen atoms. The functionalized hydrocarbon or substituted hydrocarbon has one or more substituents, as described elsewhere herein.

As used herein, the term "anhydride" is a broad term that will convey its ordinary and customary meaning to those skilled in the art (without limitation to a special or customized meaning), and refers to, but is not limited to, compositions comprising one or more anhydride groups (formula (RC (O))2O) or any compound substituted with or functionalized to include one or more anhydride groups.

As used herein, the term "sulfonic acid" is a broad term that will convey its ordinary and customary meaning to those of ordinary skill in the art (without limitation to a special or customized meaning), and refers to, but is not limited to, formic acid, acetic acid, succinic acid, lactic acid, malic acid, tartaric acid, citric acid, ascorbic acid, nicotinic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, salicylic acid, or naphthalenesulfonic acid, for example. In addition thereto, the sulfonic acid may include hydrocarbyl sulfonic acids such as aryl sulfonic acids, alkyl benzene sulfonic acids, and the like.

As used herein, the term "vegetable oil" is a broad term that will be given its ordinary and customary meaning to those of ordinary skill in the art (without limitation to a special or customized meaning), and refers to, but is not limited to, the oily fatty acid component of a plant material, such as saturated fatty acids, monounsaturated fatty acids, polyunsaturated fatty acids, and the like. The vegetable oil may be functionalized, such as alkoxylated, hydroxylated, aminated, and the like. Functionalized vegetable oils are derivatives of vegetable oils or other fatty substances, or substances with similar composition, regardless of the source of the substance. In some embodiments, the functionalized vegetable oil is an epoxidized unsaturated triglyceride. Epoxidized unsaturated triglycerides are triesters of glycerol. The glycerol is bonded to three linear or branched carboxylic acids, at least one of which comprises an epoxide moiety. For example, an epoxidized unsaturated triglyceride may be a derivative of an unsaturated fatty acid triglyceride (e.g., a vegetable or animal fat or oil) in which at least one C ═ C moiety of the parent unsaturated fatty acid triglyceride is substituted with an epoxide moiety (i.e., an oxygen-containing three-membered ring). If the parent unsaturated fatty acid triglyceride has more than one C ═ C moiety, one, some or all of the C ═ C moieties may be substituted with epoxide moieties. When the term "vegetable oil" is used herein, it is understood to include oils of animal or synthetic origin, which have the same chemical structure as vegetable oils. Examples of vegetable or animal fats or oils include coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, rapeseed oil, canola oil, safflower oil, sesame oil, soybean oil, sunflower seed oil, castor oil, tallow, and the like.

As used herein, the abbreviations for any compounds, unless otherwise indicated, conform to their common usage, accepted abbreviations, or the IUPAC-IUB Commission on Biochem.11:942-944 (1972)).

Any percentages, ratios, or other amounts mentioned herein are on a weight basis unless otherwise indicated.

The ring systems referred to herein include fused, bridged and spiro ring moieties in addition to isolated monocyclic moieties.

Examples

The following examples should not be construed as limiting the invention. The broad disclosure set forth above in the summary of the invention and the detailed description of the invention herein is repeated by reference.

Examples of products of the invention

Process for preparing liquid agricultural adjuvant concentrates

For purposes of illustration, the method of preparation of the liquid agricultural adjuvant composition (in concentrated form) used in the non-limiting examples includes the following steps: (i) mixing a portion of water and/or oil into a container, (ii) adding at least one anionic surfactant, such as sodium lauryl ether sulfate, (iii) adding at least one nonionic surfactant, such as an ethoxylated fatty alcohol, and (iv) adding at least one high terpene concentration essential oil, such as cold pressed orange oil; (v) tannic acid is added in concentrated solid form or in liquid diluted form. The process may optionally further comprise an additional step (vi): at least one additive, such as but not limited to preservatives, antioxidants, stabilizers, is added. Typically, the above steps are carried out in the order from step (i) to step (v) and optionally step (vi). The mixture was continuously stirred. Heating is not necessary, but it may be advantageous to employ heating, depending on the physical state of the individual compounds. Low or high temperatures may be employed for the particular components. The temperature may be selected to facilitate mixing over a desired period of time while avoiding degradation or undesirable reactions of the components. Other additives may also be added for specific purposes such as, but not limited to, clarifiers, defoamers, antifreeze agents, solubilizers, UV stabilizers, colorants, nutrients, amino acids, sea extracts, anti-drift agents, antifreeze agents, and water, oil or other solvents, and combinations thereof. Finally, a number of antipathogenic and/or biocidal agents can be added.

The liquid agricultural adjuvant composition may comprise ingredients in various proportions, typically, in its concentrated liquid form, the liquid agricultural adjuvant composition may comprise from about 0.1% to about 20% by weight of at least one high terpene content essential oil; about 0.1 wt% to about 25 wt% tannic acid; and from about 1% to about 50% by weight of at least one anionic surfactant; and about 1% to about 50% by weight of at least one nonionic surfactant; and about 2 wt% to about 80 wt% of water and/or other additives.

More specifically, the liquid agricultural adjuvant composition (in its concentrated liquid form) comprises 1 to 20 wt% of at least one high terpene content essential oil — preferably 2 to 10 wt%; 1 to 25 wt.% tannic acid, preferably 0.1 to 10 wt.%; 1 to 30 wt% of at least one anionic surfactant-preferably 3 to 20 wt%; 1 to 40 wt% of at least one nonionic surfactant, preferably 5 to 30 wt%; wherein the water, oil or other additives are 20 to 70 wt.%, preferably 30 to 65 wt.%. In other words, a liquid agricultural adjuvant composition weighing 100g comprises 1g to 30g of at least one high terpene content essential oil — preferably 2g to 10 g; 0.1g to 25g of tannic acid, preferably 0.1g to 10 g; 1g to 30g of at least one anionic surfactant-preferably 3g to 20 g; 1g to 40g of at least one nonionic surfactant-preferably 5g to 30 g; wherein the amount of water, oil or other additives is 20g to 70g, preferably 30g to 65 g. Any percentages, ratios, or other amounts referred to herein are on a weight gram basis unless otherwise indicated.

Preparation of liquid concentrated agricultural adjuvant compositions according to the invention

Two different liquid agricultural adjuvant compositions (in concentrated form) were prepared according to some embodiments of the present disclosure. Example 1(OR-345) and example 2(OR-346) represent concentrated agricultural adjuvant compositions. Details of the specific embodiments are shown in table 1. Different components are adopted in different preparations, including cold-pressed orange oil-natural essential oil; polyoxyethylene sorbitan monolaurate, an anionic surfactant; ethoxylated alcohol POE-6-nonionic surfactant; sodium dodecylbenzenesulfonate, an anionic surfactant; sodium lauryl ether sulfate, an anionic surfactant; ethoxylated and propoxylated alcohol EOPO 6/9, a nonionic surfactant; tannin powder.

Table 1: liquid agricultural adjuvant concentrates prepared according to the present invention

Physicochemical and accelerated stability test

Product samples of certain embodiments of the invention were analyzed to determine their physicochemical properties and performance upon dilution in water-pH, viscosity, emulsion stability, using the method described in CIPAC Handbook F-cooperative international pesticide analysis Ltd (CIPAC Handbook F-colloidal laboratory analytical Ltd)1994, redeployed 2007, the contents of which are incorporated herein by reference in their entirety. The products prepared according to the invention were determined to have accelerated storage stability and all samples were stable even under cold or warm conditions.

Table 2: test results for physicochemical Properties and accelerated stability-compositions prepared according to the invention

Method for preparing the agricultural composition (i.e., liquid fertilizer component concentrate) of the present invention as a preferred embodiment

For illustrative purposes, the method of preparation of the liquid fertilizer concentrate composition used in the non-limiting examples is carried out by the following steps: (i) mixing water or other solvents, such as alcohols or glycols; (ii) adding component fertilizers, such as salt, acid or other nutrient sources, and stirring the mixture while maintaining the temperature at 10 ℃ to 50 ℃; (iii) tannic acid is added in concentrated solid form or in liquid diluted form. The process may optionally further comprise an additional step (iv): at least one additive, such as but not limited to preservatives, stabilizers, is added. Typically, the above steps are carried out in a sequence from step (i) to step (ii) and optionally step (iv). The mixture was continuously stirred. No heating is required. For some ingredients, depending on the physical state of the compound and its enthalpy, lower temperatures or higher temperatures may occur. The temperature may be selected to facilitate mixing over a desired period of time while avoiding degradation or undesirable reactions of the components. The tannic acid is added in solid form, preferably in small amounts, to obtain a better and faster dissolution. Other additives may also be added for specific purposes, such as, but not limited to: anionic dispersants, cationic dispersants, nonionic dispersants, monomeric dispersants, polymeric dispersants, acrylic dispersants, naphthalene-based dispersants, anionic humectants, cationic humectants, nonionic humectants, naphthalene-based humectants, rheology modifiers, preservatives, antifoaming agents, antifreeze agents, stabilizers, hydrotropes (hydrotrope), stimulants, biologics, growth promoters, amino acids, hormones, solvents or co-solvents, nutrients and even water, oil or other solvents and combinations thereof. Finally, any of a number of antipathogenic and/or biocidal agents can be added.

Examples of liquid fertilizer compositions according to the invention include formulations of liquid solutions or concentrated suspensions. Other processes and equipment may be used to produce liquid, fluid or gel fertilizers, such as wet milling, chelating, complexing, solubilizing, crystallizing, gelling, and the like.

Method for preparing the agricultural composition (i.e., solid fertilizer component concentrate) of the present invention as a preferred embodiment

For illustrative purposes, the method of preparation of the solid fertilizer component concentrate used in the non-limiting examples is carried out by the following steps: (i) mixing fertilizer ingredients, such as salt, acid or other fertilizer nutrient sources, in a belt mixer; (ii) adding a dispersing agent; (iii) or adding a humectant; (iv) or adding an anti-caking agent; (v) adding tannic acid powder or liquid solution; (vi) the mixture was blended while maintaining the temperature from 25 ℃ to 40 ℃. If humidity control is required, heating is required. For some ingredients, depending on the type of compound and its enthalpy, lower temperatures or higher temperatures may occur. The temperature may be selected to facilitate blending over a desired period of time while avoiding degradation of the ingredients or undesirable agglomeration. The tannic acid is preferably added in a small amount in solid form to obtain better and faster mixing. Other additives may also be added for specific purposes, such as, but not limited to: anionic dispersants, cationic dispersants, nonionic dispersants, monomeric dispersants, polymeric dispersants, acrylic dispersants, naphthalene-based dispersants, anionic humectants, cationic humectants, nonionic humectants, naphthalene-based humectants, rheology modifiers, preservatives, antifoaming agents, anticaking agents, binders, coating agents, disintegrants, fillers, flow agents, stabilizers, hydrotropes (hydrosopes), stimulants, biologicals, growth agents, amino acids, hormones, solvents or co-solvents, nutrients, and even water. Finally, any of a number of antipathogenic and/or biocidal agents can be added.

Examples of solid fertilizer compositions according to the present invention include formulations of soluble powders. Other processes and equipment can be used to produce the solid fertilizer composition, for example, mixers, crushers, blenders, V-mixers, drum mixers, fluidized beds, granulators, ball mills, extruders, spray dryers, grinders, air mills, hammer mills, roll mills, ball mills, bead mills, liquid bead mills (coating machines), and the like.

Preparation of agricultural compositions as fertilizer compositions

Various formulations of fertilizer compositions containing tannic acid were produced to illustrate various examples within the scope of the present invention. Various ingredients are used in various compositions, including industrial urea (urea technical) -urea (45% nitrogen); tannic acid-tannic acid (at least 70% tannic acid); tannic acid solution-tannic acid content in water 33%; potassium carbonate- (66% K2O); EDTA 2-disodium-EDTA disodium; copper EDTA — copper EDTA chelate (14% copper); 325 mesh micronized manganese carbonate (43% manganese); micronized calcium carbonate- (40% calcium); phosphoric acid- (61.6% of P2O 5); boric acid- (19% boron); sodium hydroxide solution (50% sodium hydroxide) -a neutralizing agent; propylene glycol-an anti-freeze humectant; xanthan gum 230, a rheology modifier; ethoxylated fatty alcohols-nonionic moisturizers; alkylated sulfonates-anionic humectants and dispersants; graft copolymer-polymeric dispersant; naphthalene sulfonate condensate-naphthalene dispersant; lignosulfonate-an anionic dispersant; alkylated sulfonates-anionic humectants; benzisothiazolinone-preservative.

Examples 3 to 6-major and minor nutrients-Nitrogen (N), phosphorus (P), Potassium (K), calcium (Ca), magnesium (Mg) and Sulfur (S)

Example 3-liquid fertilizer composition containing nitrogen, boron and tannic acid according to the invention comprising: 6.8% of industrial urea, 1.2% of boric acid, 10.0% of tannic acid solution 33% and 6.0% of nonionic humectant; 10.0% of anionic humectant and dispersant; 66.0% water and other additives. The final fertilizer composition was guaranteed to be 3.0% nitrogen, 0.2% boron.

Example 4-liquid fertilizer composition containing potassium and tannic acid according to the invention comprising: 38.0 percent of potassium carbonate, 9.0 percent of tannic acid solution and 4.0 percent of anti-freezing humectant; 54.0% water, preservatives, xanthan gum and other additives. The final fertilizer composition ensured 25% potassium (as K2O).

Example 5-liquid fertilizer composition containing calcium and tannic acid according to the invention comprising: 52% of 325-mesh micronized calcium carbonate, 8.0% of tannic acid solution 33%, and 8.0% of polymer dispersant; 5.0% of an antifreeze agent; 27% water and other additives. The final fertilizer composition ensured 15.0% calcium.

Example 6-liquid fertilizer composition containing sulphur and tannic acid according to the invention comprising: 42.0% 325 mesh micronized elemental sulfur, 8.0% tannic acid solution 33%, 3.0% polymeric dispersant; 5.0% of an antifreeze agent; 2% of a cationic dispersant; 40.0% water and other additives. The final fertilizer composition ensured 40.0% sulfur.

Examples 7 to 10-micronutrient Components-boron (B), copper (Cu), manganese (Mn) and Zinc (Zn)

Example 7-liquid fertilizer composition containing boron and tannic acid according to the invention comprising: 44.0% boric acid, 12.0% monoethanolamine, 10.0% tannic acid solution 33%; 34.0% of water and other additives. The final fertilizer composition ensured 8% boron (B).

Example 8-liquid fertilizer composition containing boron and tannic acid according to the invention comprising: 44.0% boric acid, 50% of 9.0% sodium hydroxide solution, 33% of 10.0% tannic acid solution; 37.0% of water and other additives. The final fertilizer composition ensured 8% boron (B).

Example 9-a copper-containing solid fertilizer composition according to the invention comprising: 87% of copper chelate; 6% of tannic acid; 4.0% of an anionic dispersant; 3% of other additives. The final fertilizer composition ensured 12.0% copper (Cu).

Example 10-liquid fertilizer composition containing manganese and tannic acid according to the invention comprising: 35.0% 325 mesh micronized manganese carbonate, 8.0% tannic acid solution 33%, 5.0% antifreeze and wetting agent; 5.0% polymeric dispersant; 47.0% water, preservatives, xanthan gum and other additives. The final fertilizer composition ensured 15.0% manganese (Mn).

Fertilizer composition boron (B) -OR-198 used in field test

OR-198-a liquid fertilizer composition containing boron and tannic acid according to the invention comprising: 44.0% boric acid, 12.0% monoethanolamine, 43.0% water and other additives. The final fertilizer component ensured 8% boron (B).

Fungicide compositions-copper oxychloride and Sulfur for field trials

OR-210-liquid fertilizer Suspension Concentrate (SC) composition containing copper oxychloride comprising: 26.0% copper oxychloride; 4.0% of a naphthalene dispersant; 2.0% polymeric dispersant; 5.0% of other additives such as antifreeze, humectant, thickener, preservative; and about 63% water. The final fertilizer composition was guaranteed to be 260g/L copper oxychloride.

OR-161-B-3-a-liquid fertilizer Suspension Concentrate (SC) composition containing elemental sulphur comprising: 46.0% elemental sulphur; 3.0% of a naphthalene dispersant; 3.0% polymeric dispersant; 5.0% of other additives such as antifreeze, humectant, thickener, preservative; and about 43% water. The final fertilizer composition was guaranteed to be 575g/L sulfur.

Physicochemical and accelerated stability test

Product samples of certain embodiments of the invention were analyzed to determine their physicochemical properties and performance upon dilution in water, pH, viscosity, particle size distribution and suspensibility, using the method described in CIPAC Handbook F-cooperative international pesticide analysis Ltd (CIPAC Handbook F-colloidal laboratory pesticide analytical Ltd)1994, redeployed 2007, the contents of which are incorporated herein by reference in their entirety. The products prepared according to the invention were determined to have accelerated storage stability and all samples were stable even under cold or warm conditions.

Table 3: fertilizer compositions according to the invention containing primary and secondary nutrients and tannins-physical, chemical and accelerated stability test results

Table 4: micronutrient compositions of the invention-results of physicochemical and accelerated stability tests

Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity and understanding, it will be readily apparent to those of ordinary skill in the art that certain changes and modifications may be practiced. Therefore, the description and examples should not be construed as limiting the scope of the invention to the particular embodiments and examples described herein, but rather as encompassing all modifications and alterations consistent with the true scope and spirit of the invention.

Field test and laboratory test-recovery evaluation method

Field trials (field trials) were conducted for more than 3 years at 2 sites in brazil to evaluate and finally demonstrate that plant health was improved and maintained by applying a composition and treatment method consisting of a fertilizer solution of one or more nutrients and a portion of tannic acid added to the solution to control phytopathogens and endophytes (Candidatus Liberibacter in citrus plants) to promote vascular dilation of plant tissue and/or to promote the clearance of bacterial colonies from vascular plant tissue, thereby restoring the level of photosynthesis, fruit and plant health of the treated trees.

The purpose of these studies was to assess and measure the recovery of the symptoms of Huanglongbing (HLB), a disease caused by the colonization of the phlobacterium (Candidatus Liberibacter) in the phloem and xylem vessels, after spraying the different formulations of the invention and their mixtures with other formulations. Finally, the selected formulation, OR-198-A, showed surprising results. The field trial will continue until 1095 days after treatment (3 years after starting treatment).

Codes and products used during field trials:

a) OR-198-A-example 7 of the invention-a tannic acid containing monoethanolamine borate (boron 8.0 wt/wt%);

b) OR-198-B-example 8 of the invention-a tannin containing fertilizer based on sodium borate (boron 8.0 wt/wt%);

e) OR-345-example 1 of the invention-essential oil and tannic acid based adjuvants;

f) OR-210-a fungicide based on 260.0g/L copper oxychloride;

g) OR-161-B-3-A-a fungicide based on 585.00g/L sulfur;

h)-a commercially available adjuvant based on orange oil and ethoxylated alcohol;

f) OR-198-commercial fertilizer based on monoethanolamine borate (boron 8.0 wt/wt%).

Position: the test was performed in 2017 and 2018 at alagass (arabongas, Paran a, Brazil) in barrena, Brazil, with the location under the geographic coordinate system: latitude: -234164769, longitude: 515126852, Agrobis farm, 91A plot. The citrus variety is "Pera Rio" 10 year old. The nutrient analysis in the soil for which both tests were carried out is described in table 5.

TABLE 5 soil analysis (nutrient level and physical analysis), alagakas-2018, Balana, Brazil

Experimental design and plots: two experiments were performed on the same farm, and the experimental Design used a Random Block Design (Random Block Design). The first trial consisted of 10 treatment groups and the second trial consisted of 13 treatment groups, both trials having 4 replicates. Plot size consisted of 5 plants in a row each, evaluating only the plot center, and the remaining plants as physical barriers to reduce the risk of contamination for other treatments. A total of 200 citrus fruit plants were used in the first experiment and 260 citrus fruit plants were used in the second experiment.

Spray application: the spray was carried out using a knapsack sprayer (model: Stihl SR 450) using a water volume of 1200L.ha-1 to match the custom practice used by citrus growers.

Processing table: the treatment methods used in both experiments, as well as the dates and growth stages on which the treatments were performed, are shown in table 7. The spray application interval was 15 days and two trials were sprayed a total of 6 times. Commercial penetrant adjuvants were used for all treatmentsThe ratio was 500mL c.p.ha-1

Evaluation: photosynthesis, transpiration, fruit diameter, fruit weight, fruit juice content and Brix were evaluated in two experiments. For photosynthesis and transpiration, 4 evaluations were performed in each trial, with only one evaluation of fruit diameter and weight in all replicates.

To measure photosynthesis, a device called "minippm" was used, and the collected data set was calculated and submitted to calculation to determine an estimate of photosynthetic rate according to the following formula: P-Q x Φ P x PAR, calculated in micromoles/m 2/s. Evaluations are also made prior to dawn to determine the "Fref" value to calculate the "Q" coefficient.

To measure transpiration, a device called a "stomatometer" was used in the test, and the device was calibrated for each evaluation according to the manufacturer's standards.

Fruit set (fruit set) estimates are established by calculating the total real fruit number per tree within each plot. After the plot was harvested, 12 fruit samples were taken from the harvested fruits and then the weight and fruit size were measured.

The juice content and brix were determined by extracting the juice content from 12 fruits randomly harvested from each plot during the harvest stage of the fruit ripening stage. The whiteness was measured with a refractometer.

PCR (polymerase chain reaction) tests were also performed to assess and confirm the presence of the bacterium, Brevibacterium (Candidatus Liberibacter), in product-treated and non-product-treated plants.

Statistical analysis: the data sets obtained in both experiments were submitted to a homogeneity of variance study (to stabilize or reduce existing variability) by the Box-Cox method. Since the data do not exhibit normal distributions, the conversion is performed according to a logarithmic model. The data sets were then submitted to analysis of variance and Tukey tests compared the mean when significant at the 5% probability level. The SASM Agri program is used to analyze a data set.

Experiment #1

Photosynthesis (mu mol/m)2/s)

Observing the data shown in Table 6, it is noted that the photosynthetic rate values before the first spray treatment (μmol/m) established by the experiment were determined by statistical analysis2S) are equal, indicating that the photosynthetic parameters of the plants, plots and blocks are consistent. Initial assessments were made at 2017 on day 8, 25.

At 10 days after the first spray on day 4, 9/2017, homogeneity of the treatment groups could still be observed based on statistical analysis, which allowed one to conclude that there were no relevant differences in this parameter, and that any treatment was considered to be sufficiently effective.

However, the treatment groups showed significant differences, mainly relative to the control (plots without spray) evaluated 41 days after the first spray, 2017, 10 months and 5 days. Significant differences were observed indicating that the most effective treatment groups were OR-198-A (1000mL. ha-1) and a mixture of OR-198-A + OR-210 OR OR-198-A + OR-161-B-3-A. A trend towards better results was observed with a rate factor (rate factor) for isolating OR-198-A when a mixture of OR-198-A + OR-161-B-3-A was used.

A significant increase in photosynthetic rate was also observed for evaluation 75 days after the first spray, and there was an improvement in this parameter, mainly when using the OR-198-a + OR-161-B-3-a mixture.

TABLE 6 photosynthetic rates measured during the experiment #1 procedure, Alabagas 2017/2018, Balana, Brazil

Mean values of subsequent identical letters in the column were statistically not different with a probability of 5% by Tukey test.

All treatments were usedThe ratio was 500mL c.p.ha-1

Transpiration (mol/m)2/s)

Table 7 shows the average of the measured transpiration of citrus leaves in the field before the start of spraying and after the spraying sequence.

It was observed that the mean values in the initial evaluations carried out on day 25 of 8 months in 2017 were statistically equal, demonstrating the homogeneity (homogeneity) of the plot set up for the treatment.

Treatment resulted in a tendency to increase transpiration, particularly with OR-198-A + OR-161-B-3-A.

TABLE 7 Transpiration (TR) measured during the course of experiment #1, Allapagacas 2017/2018, Balana, Brazil

Mean values of subsequent identical letters in the column were statistically not different with a probability of 5% by Tukey test.

All treatments were usedThe ratio was 500mL c.p.ha-1

Fruit diameter, fruit weight, fruit juice content and brix

Table 8 shows the average values of fruit diameter and fruit weight. Positive growth was noted in all treatment groups.

Evaluation of the juice content of each fruit showed a significant increase in juice content for all treatment groups, but the most effective spray was a mixture of OR-198-A + OR-210 OR OR-161-B-3-A. It also shows an increase in brix.

TABLE 8 fruit diameter (mm), fruit weight (g), fruit juice content per fruit (g) and Brix measured during experiment (test) #1 procedure, Alabangas 2017/2018, Balana, Brazil

Mean values of subsequent identical letters in the column were statistically not different with a probability of 5% by Tukey test.

All treatments were usedThe ratio was 500mL c.p.ha-1

Fruit parameters and yield parameters

According to table 9, application of OR-198-a affects fruit parameters (e.g. diameter and fruit height) as well as the number of seeds per fruit. For fruit diameter, the interaction between OR-198-A and OR-161-B-3-A was positive in this experiment. The best results were obtained with OR-198-A alone, in terms of fruit height. Regardless of which treatment is used, the average seed number per fruit is significantly affected by the treatment.

Significant incremental responses were also verified by analysis of variance and mean separation tests for yield parameters (table 10). When sprayed with OR-198-a (alone) OR in a tank mix containing OR-210 OR-161-B-3-a, the fruit set rate per tree was significantly affected, but a more significant response was shown in the mix of OR-161-B-3-a. In both cases, the average fruit weight experienced an incremental response, either alone or in a pot mix.

Yield was also significantly affected by treatment (application of OR-198-a alone OR in a tank mix) in response to significant increases in fruit set rate and average fruit weight level. However, OR-198-A applied in a mixture with OR-161-B-3-A has a tendency to outperform other treatments as compared to other treatments. The relative increase rates of yield for the application of OR-198-A, OR-198-A + OR-210 and OR-198-A + OR-161-B-3-A were 11.7%, 22.8% and 30.2%, respectively.

TABLE 9 fruit parameters and yield parameters during the experiment #1 procedure, Alabangas 2017/2018, Balasa, Brazil

Mean values of subsequent identical letters in the column were statistically not different with a probability of 5% by Tukey test.

All treatments were usedThe ratio was 500mL c.p.ha-1

PCR results

Based on the summary results of the PCR analysis, most plots showed the presence of Brevibacterium (Candidatus Liberibacter). Without being bound by theory, when bacteria have colonized the sap conduit, the treatment will significantly restore the photosynthesis parameters/variables, which means that the symptoms will be alleviated even if the plant has become ill.

TABLE 10 PCR test for the Presence or absence of Brevibacterium (Candidatus Liberibacter)

(red) ═ detection of brevibacterium (Candidatus Liberibacter). No mycobacterium phlorhizium (Candidatus Liberibacter) was detected.

All treatments were usedThe ratio was 500mL c.p.ha-1

Experiment #2

Photosynthesis (mu mol/m)2/s)

The average of the light combination rates in the second set of experiments is shown in table 11. It can be observed that, as in experiment 1, the plots were under homogenous conditions, the previous evaluations were carried out in 2017, 6 and 9 days, and there were no significant differences between them, thus providing reliability to the results of the subsequent evaluations after treatment.

At 29 days post-application (DAA), a positive difference in photosynthetic rate was detected, taking into account the proposed statistical analysis. This allows us to conclude that the treatment used in this evaluation is sufficiently effective to increase the level of photosynthesis in the citrus plant being treated. It is noteworthy that, although the first evaluation was performed after one application, it has been noted that, in this case, the combination of OR-198-A + OR-161-B-3-A increased the level of photosynthesis to a higher level.

Considering the evaluation of 63DAA, the difference becomes larger, further demonstrating that treatment means an increase in photosynthesis. This is particularly evident in the mixture of OR-198-A + OR-161-B-3-A. Statistical analysis between products OR-198-A and OR-198-B gave similar values considering the same evaluation date and isolated product usage.

In the evaluation of 96DAA, when there is a correlation between the products OR-198-A + OR-161-B-3-A, the values can still be highlighted, thus showing possible interactions between the products in the photosynthesis parameters.

TABLE 11 photosynthetic rates measured during the experiment #2 procedure, Alabagas 2017/2018, Balana, Brazil

Mean values of subsequent identical letters in the column were statistically not different with a probability of 5% by Tukey test.

Transpiration (mol/m)2/s)

Next, the average value of leaf transpiration was estimated by a "stomatometer" according to the evaluation of Table 12.

As in experiment #1, there was a positive increase in transpiration observed by spray application of the treatment groups. Transpiration is complex and, without being bound by theory, it is believed that more progress may be associated with increased photosynthesis, not just the transpiration rates shown in the two experiments.

TABLE 12 Transpiration (TR) measured during the course of experiment #2, Alpagagagas 2017/2018, Balana, Brazil

Mean values of subsequent identical letters in the column were statistically not different with a probability of 5% by Tukey test.

Fruit diameter and fruit weight

From table 13, the calculated average values of fruit diameter and fruit weight can be observed.

For fruit diameter, an increase was observed when the treatment was applied. The most significant results were obtained with the combination of spraying OR-198-A + OR-161-B-3-A.

For fruit weight, an increase was also observed, but all treatment groups were statistically identical.

The treatments performed in the experiments had a significant effect on the juice content (juice content). The most significant results were obtained when the mixture OR-198-A + OR-161-B-3-A was applied.

TABLE 13 fruit diameter (mm) and fruit weight (g) measured during experiment #2 procedure, alagakas 2017/2018, Balana, Brazil

Mean values of subsequent identical letters in the column were statistically not different with a probability of 5% by Tukey test.

Fruit parameters and yield parameters

In table 14, significant differences between the calculated averages of fruit parameters (such as diameter and height) can be observed. The increase in these variables is affected by the application, primarily by the product OR-198-B and the tank mix OR-198-A + OR-161-B-3-A. The average seed number per fruit was significantly increased by treatment, with the interaction of OR-198-A + OR-161-B-3-A being more responsive.

Significant incremental responses were also verified by analysis of variance and mean separation tests for yield parameters (table 14). The fruit set rate per tree increased when the application was completed, particularly when the pot mix OR-198-A + OR-161-B-3-A was used. For fruit weight, application of OR-198-B OR OR-198-A + OR-161-B-3-A was sufficiently effective to elicit an incremental response in this variable.

Depending on the variables analyzed (fruit set rate and fruit weight), yield was affected by the treatment application, and the best results obtained in this experiment were the pot mix OR-198-A + OR-161-B-3-A and OR-198-B, OR-198-B applied separately. For OR-198-A, OR-198-B, OR-161-B-3-A and OR-198-A + OR-161-B-3-A, the relative yield increases of the second experiment were 23.5%, 28.0%, 4.3% and 35.2%, respectively.

TABLE 14 fruit parameters and yield parameters during the experiment #2 procedure, Alabangas 2017/2018, Balana, Brazil

PCR results

In the same manner as experiment #1, most plots showed the presence of B.phloretin (Candidatus Liberibacter). However, the repeated results of photosynthesis in both experiments showed that spraying of the treatment groups favoured the recovery of HLB symptoms. Accordingly, the above disclosure provides methods of controlling and/or treating and/or inhibiting HLB in citrus plants.

TABLE 15 PCR test (test #2) for the presence or absence of B.phlorizae (Candidatus Liberibacter)

(red) ═ detection of brevibacterium (Candidatus Liberibacter). No mycobacterium phlorhizium (Candidatus Liberibacter) was detected.

From the results obtained and explained in experiments 1 and 2, the following conclusions can be drawn:

a) spraying of the OR-198A and B formulations has a responsive and positive impact (positive) on parameters such as photosynthesis, fruit size, fruit weight, fruit set rate, fruit juice content and yield, and can alleviate HLB symptoms.

b) While spraying the OR-198-a formulation, it is recommended to mix the OR-161-B-3-a formulation to obtain a higher physiological result, and thus a more pronounced result (expressed result);

c) it is recommended to use 2000mL.ha-1 to 3000mL.ha-1 of OR-198 formulation.

d) Compared to the commercial adjuvant + OR-198 formulation, it is recommended to use OR-345 (tannic acid) + OR-161-B-3-A + OR-198.

It is noted that the use of the product of the invention produces a very good and unexpected concomitant effect, whereby a significant increase in insect control (e.g. a reduction in the number of psyllids at all stages (eggs, nymphs and adults)) and an improvement in other disease control (e.g. a reduction in citrus rust mite (rust mite), leprosy mite (leprosy mite) and black spot (black spot) damage) is observed. Field trials were conducted in some locations in brazil and the united states, as well as on other types of trees (e.g., grapes, olives) and some fruits and vegetables, to demonstrate the performance of the products of the invention.

The field trials contracted and operated by official agencies in brazil, usa and china are examples, and in brazil and several parts of the usa, field trial evaluations were carried out with long-term field trials to demonstrate the recovery and control of green-discoloration.

Fig. 10 shows an electron micrograph through citrus leaves, where (a) shows a cross-section of an untreated citrus plant having HLB, and where (b) shows a cross-section of a citrus plant having HLB but treated with an agricultural composition of the invention. (a) Showing bacterial blockage in the vascular system as indicated by the arrow, (b) showing improvement in bacterial blockage in the vascular system after treatment using an embodiment of the invention with formulation number ORO-345 as described above. Clearly, the present invention improves vascular disease, particularly HLB, in citrus plants.

While the disclosure has been illustrated and described in detail in the drawings and foregoing description, such illustration and description are to be considered illustrative or exemplary and not restrictive. The present disclosure is not limited to the disclosed embodiments. Variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed disclosure, from a study of the drawings, the disclosure, and the appended claims.

All cited documents are hereby incorporated by reference in their entirety. If publications and patents or patent applications incorporated by reference contradict the disclosure contained in the specification, the specification is intended to defer and/or override any contradictory material.

Unless otherwise defined, all terms (including technical and scientific terms) are to be given their ordinary and customary meaning to one of ordinary skill in the art, and are not to be limited to a specific or customized meaning unless explicitly defined herein. It should be noted that the use of particular terminology when describing certain features or aspects of the disclosure should not be taken to imply that the terminology is being re-defined herein to be restricted to including any specific characteristics of the features or aspects of the disclosure with which that terminology is associated. The terms and phrases used in this application, and variations thereof, especially in the appended claims, should be construed to be open ended and not limiting unless otherwise expressly stated. As examples of the foregoing, the term 'including' should be understood as 'including, without limitation', etc.; as used herein, the term 'comprising' is synonymous with 'including', 'containing', or 'characterized by', and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps; the term 'having' should be interpreted as 'having at least'; the term 'including' should be interpreted as 'including but not limited to'; the term 'examples' is used to provide illustrative examples of the items in question, and is not an exhaustive or limiting list; adjectives such as 'known', 'normal', 'standard' and terms of similar meaning should not be construed as limiting the item described to a given time period or to an item available at a given time, but rather should be construed to encompass known, normal, or standard techniques that may be available or known at any time now or in the future; and the use of terms such as 'preferably', 'preferred', 'desired' or 'ideal' and words of similar import should not be taken to imply that certain features are critical, essential or even important to the structure or function of the invention, but are merely intended to highlight alternative or additional features that may or may not be utilized in a particular embodiment of the invention. Likewise, a group of items linked with the conjunction 'and' should not be read as requiring that each and every one of those items be present in the grouping, but rather should be read as 'and/or' unless expressly stated otherwise. Likewise, a group of items linked with the conjunction 'or' should not be read as requiring mutual exclusivity among that group, but rather should be read as 'and/or' unless expressly stated otherwise.

Where a range of values is provided, it is understood that the upper and lower limits and each intervening value between the upper and lower limits of that range is encompassed within the embodiments.

With respect to substantially any plural and/or singular terms used herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. Various singular/plural permutations may be expressly set forth herein for the sake of clarity. The indefinite article "a" or "an" does not exclude a plurality. The indefinite article "a" or "an" does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. Any reference signs in the claims shall not be construed as limiting the scope.

It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles "a" or "an" limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases "one or more" or "at least one" and indefinite articles such as "a" or "an" (e.g., "a" and/or "an" should typically be interpreted to mean "at least one" or "one or more"); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should typically be interpreted to mean at least the recited number (e.g., the bare recitation of "two recitations," without other modifiers, typically means at least two recitations, or two or more recitations). Further, in those instances where a convention analogous to "at least one of A, B and C, etc." is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B and C" would include but not be limited to systems having a alone, B alone, C, A and B together, a and C together, B and C together, and/or A, B and C together, etc.). In those instances where a convention analogous to "A, B or at least one of C, etc." is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B or C" would include but not be limited to systems having a alone, B alone, C, A and B together alone, a and C together, B and C together, and/or A, B and C together, etc.). It will be further understood by those within the art that virtually any disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase "a or B" will be understood to include the possibility of "a" or "B" or "a and B".

All numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification are to be understood as being modified in all instances by the term 'about'. Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties sought to be obtained. And not as an attempt to limit the application of the doctrine of equivalents to the scope of any claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques in any application claiming priority to this application.

Furthermore, although the foregoing has been described in some detail by way of illustration and example for purposes of clarity and understanding, it will be readily apparent to those of ordinary skill in the art that certain changes and modifications may be practiced. Therefore, the description and examples should not be construed as limiting the scope of the invention to the particular embodiments and examples described herein, but rather as encompassing all modifications and alterations consistent with the true scope and spirit of the invention.

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