Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
09718739 ยท 2017-08-01
Inventors
Cpc classification
C05G3/60
CHEMISTRY; METALLURGY
International classification
A01N25/24
HUMAN NECESSITIES
Abstract
A pesticide, fungicidal, bactericidal, anti-pathogen or biocidal composition includes at least one biologically inert carrier; and at least one doped component including at least one fixed copper compound doped with at least one compound selected from the group consisting of iron compounds, zinc compounds, magnesium compounds, calcium compounds, and combinations and/or mixtures thereof. In one embodiment, the doped component has a particle size of about 0.5 nm to about 30 microns. A method for the control of pests includes the step of applying to the pests or their growth habitat the aforementioned composition. The method also includes the control of disease in citrus plants caused by vectors such as Psyllid nymphs, by applying the aforementioned composition to their growth habitat in citrus groves.
Claims
1. A method for controlling pests wherein said pests is at least one fungus in a plant and said method comprises applying to said at least one fungus or its growth habitat where said fungus is to be present a fungicidal composition comprising, a) at least one biologically inert carrier; and b) at least one doped component comprising at least one fixed copper compound doped with at least one compound selected from the group consisting of iron compounds, zinc compounds and combinations thereof, said at least one doped component is incorporated into the structure of said fixed copper compound; said method comprising applying said fungicidal composition in an effective amount for treating fungal diseases in plants, wherein said iron compound is an insoluble or substantially insoluble iron compound; wherein said iron compound is selected from the group consisting of iron hydroxide, iron oxyhydroxide, iron oxide, iron glucose, ferric citrate, Ferritin, ferrous fumarate, ferrous sulfate, and iron saturated human holotransferrin.
2. A method for controlling pests wherein said pests is at least one fungus in a plant and said method comprises applying to said at least one fungus or its growth habitat where said fungus is to be present a fungicidal composition comprising, a) at least one biologically inert carrier; and b) at least one doped component comprising at least one fixed copper compound doped with at least one compound selected from the group consisting of iron compounds, zinc compounds and combinations thereof, said at least one doped component is incorporated into the structure of said fixed copper compound; said method comprising applying said fungicidal composition in an effective amount for treating fungal diseases in plants, wherein said fixed copper compound is cupric hydroxide and said iron compound is iron hydroxide and/or iron oxyhydroxide.
3. A method for controlling pests wherein said pests is at least one fungus in a plant and said method comprises applying to said at least one fungus or its growth habitat where said fungus is to be present a fungicidal composition comprising, a) at least one biologically inert carrier; and b) at least one doped component comprising at least one fixed copper compound doped with at least one compound selected from the group consisting of iron compounds, zinc compounds, and combinations thereof, said at least one doped component is incorporated into the structure of said fixed copper compound; said method comprising applying said fungicidal composition in an effective amount for treating fungal diseases in plants; said method further comprising: c) at least one iron compound is mixed with a) and b); wherein said iron compounds is at least one insoluble or substantially insoluble iron compound; wherein said iron compounds comprises iron hydroxide.
4. The method of claim 3, wherein said fungicidal composition is administered to fungi or their growth habitat by a method selected from the group consisting of dusting, sprinkling, spraying, brushing, dipping, smearing, impregnating, injection of the composition into plant vasculature, and application to a root system.
5. A method for controlling pests wherein said pests is at least one fungus in a plant and said method comprises where said fungus is to be present applying to said at least one fungus or its growth habitat a where said fungus is to be present a fungicidal composition comprising, a) at least one biologically inert carrier; and b) at least one doped component comprising at least one fixed copper compound doped with at least one compound selected from the group consisting of at least one iron compound, at least one zinc compound and combinations thereof; said at least one doped component is incorporated into the structure of said fixed copper compound; said at least one fixed copper compound being copper hydroxide or copper oxide, or combinations thereof; said method comprising applying said fungicidal composition in an effective amount for treating fungal diseases in plants.
6. The method of claim 5, wherein said fixed copper compound is selected from the group consisting of cupric hydroxide, copper oxychloride, copper oxide, cupric carbonate basic, copper sulfate basic, tribasic copper sulfate, cuprous oxide, cupric citrate, cupric phosphate, cuprobam, indigo copper, minerals brochantite, langite, malachite, cornetite, libethenite, pseudolibethenite, pseudo-malachite, antlerite, covellite, marshite, cuprite, chalcocite, Rogojski's salt, brochantite, hydrocyanite, nantokite, dolerophane, ammonia copper carbonate, basic copper chloride, and combinations thereof.
7. The method of claim 6, wherein said fixed copper compound is cupric hydroxide.
8. The method of claim 5, wherein said iron compound is an insoluble or substantially insoluble iron compound.
9. The method of claim 5, wherein said zinc compound is an insoluble or substantially insoluble zinc compound.
10. The method of claim of claim 9, wherein said zinc compound is selected from the group consisting of zinc hydroxide and zinc oxide.
11. The method of claim 5, wherein said doped component includes about 15 at % iron from said iron compound doped within said fixed copper compound.
12. The method of claim 5, wherein particle size of said doped component is about 3.5 to about 200 nm.
13. The method of claim 12, wherein said particle size of said doped component is about 3.5 to about 10 nm.
14. The method of claim 5, wherein said fungicidal composition includes a fixed copper compound having a particle size of about 3.5-10 nm.
15. The method of claim 5, wherein said fungicidal composition is administered to fungi or their growth habitat by a method selected from the group consisting of dusting, sprinkling, spraying, brushing, dipping, smearing, impregnating, injection of the composition into plant vasculature, and application to a root system.
16. The method of claim 5, wherein said doped component is only doped with an iron compound and a zinc compound.
17. The method of claim 5, further comprising c) at least one iron compound mixed with a) and b).
18. The method of claim 17, wherein said iron compound is at least one insoluble or substantially insoluble iron compound.
19. The method of claim 17, further comprising d) at least one zinc compound mixed with a), b) and c).
20. The method of claim 19, wherein said at least one zinc compound is an insoluble or substantially insoluble zinc compound.
21. The method of claim 20, wherein said at least one zinc compounds is zinc hydroxide or zinc oxide.
22. The method of claim 5, further comprising at least one zinc compound mixed with a) and b).
23. The method of claim 22, wherein said at least one zinc compound is an insoluble or substantially insoluble zinc compound.
24. The method of claim 23, wherein said at least one zinc compounds is zinc hydroxide or zinc oxide.
25. The method according to claim 5 wherein said doped component has a particle size of about 0.5 nm to 30 microns.
26. The method of claim 25, wherein said zinc compound is an insoluble or substantially insoluble zinc compound.
27. The method of claim 25, wherein said-zinc compound is selected from the group consisting of zinc hydroxide and zinc oxide.
28. A method for controlling of pests wherein said pests is at least one fungus in a plant and said method comprises applying to said at least one fungus or its growth habitat where said fungus is to be present a fungicidal composition comprising, a) at least one biologically inert carrier; and b) at least one doped component comprising at least one fixed copper compound doped with at least one compound selected from the group consisting of iron compounds, zinc compounds, and combinations thereof, said at least one doped component is incorporated into the structure of said fixed copper compound; said method comprising applying said fungicidal composition in an effective amount for treating fungal diseases in plants.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The preferred embodiment of the present invention can best be understood in connection with the accompanying drawing. It is noted that the invention is not limited to the precise embodiments shown in drawings, in which:
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DETAILED DESCRIPTION OF THE INVENTION
(6) The invention is a pesticide, fungicidal, bactericidal, anti-pathogen or biocidal composition comprising a) at least one biologically inert carrier; and b) at least one doped component including at least one fixed copper compound doped with at least one compound selected from the group consisting of iron compounds, zinc compounds, magnesium compounds, calcium compounds and combinations thereof. In a preferred embodiment, the doped component only includes iron compounds and/or zinc compounds as the only doping compound. For example, copper hydroxide may be doped with iron hydroxide, iron oxyhydroxide or other iron compound as one doped component. In one embodiment, the fixed copper compound is doped with an insoluble iron compound, wherein the fixed copper compound is partially substituted by the insoluble iron compound. The invention also comprises a fixed copper compound, such as copper hydroxide, doped with a zinc compound. Furthermore, the fixed copper compound, such as copper hydroxide, may be doped with both an iron compound and a zinc compound. Applicant's invention includes at least one doped component containing both the fixed copper compound doped with an iron compound and/or a zinc compound that can be used similarly to how copper hydroxide alone is used. In one embodiment of the present invention, an iron compound is doped on copper hydroxide, a zinc compound is doped on copper hydroxide, a zinc compound and an iron compound are doped on copper hydroxide, singly and optionally combined together, and or added to other pesticide agents. The doped component is prepared according to methods described herein and readily understood to those of skill in the art. The composition can be used in many of the applications that copper hydroxide is currently utilized, and many new pesticidal indications which are currently resistant to copper. See, for example, WO2006028853. In a preferred embodiment, copper hydroxide is doped with iron hydroxide to provide 15 at % iron to the doped component, which results in a black doped component. In another preferred embodiment, the atomic percentage (at %) of iron in the doped component is less than 15 at %, more preferably less than 10 at %. Because of the increased biocidal activity, the preferred copper hydroxide-iron hydroxide doped component prepared by the present method is especially useful as an active ingredient in pesticides, fungicides, bactericides and biocides. This increased biocidal activity reduces the number of pathogens currently resistant to copper pesticides, increasing the range and breath of activity of copper against other bacteria, fungi, viruses, mycoplasma, and other pathogenic organisms.
(7) Preferably, the composition is administered to plants by a method selected from the group consisting of dusting, sprinkling, spraying, brushing, dipping, smearing, impregnating, injection of the composition into plant vasculature, and application to a root system.
DEFINITIONS
(8) In the context of this application, several terms are utilized as follows:
(9) The definition of pesticide used in this application refers to the United States EPA definition page 1 of www.epa.gov/agriculture/tpes.html which is A pesticide is any substance or mixture of substances intended for preventing, destroying, repelling, or mitigating any pest. Pests can be insects and insect-like organisms, mice and other vertebrate animals, unwanted plants (weeds), or fungi, bacteria and viruses that cause plant diseases. Though often misunderstood to refer only to insecticides, the term pesticide also applies to herbicides, fungicides, and various other substances used to control pests.
(10) The definition of a mixture: a mixture contains 2 or more substances that are not chemically combined. Mixtures are unlike chemical compounds, because: the substances in a mixture can be separated using physical methods such as filtration and distillation. Mixtures have variable compositions while compounds have a fixed definite formula. When mixed, individual substances keep their properties in a mixture, while if they form a compound their properties can change. See http://www.chemicool.com/definition/mixture.html). An example of a mixture is NORDOX 30/30 wg, manufactured by NORDOX AS c/o Monterey AgResources, EPA Reg. No. 48142-7), which is a cuprous oxide and zinc oxide mixture.
(11) The definition of elements and compounds: Elements and compounds are pure chemical substances found in nature. The difference between an element and a compound is that an element is a substance made of the same type of atoms, whereas a compound is made of different elements in definite proportions. Examples of elements include iron, copper, zinc, hydrogen and oxygen. Examples of compounds include water (H.sub.2O) and salt (sodium chloride-NaCl). See, http://www.diffen.com/difference/Compound_vs_Element.
(12) The definition of complex: A complex is a molecular entity formed by loose association involving two or more component molecular entities (ionic or uncharged), or the corresponding chemical species. The bonding between the components is normally weaker than in a covalent bond. In inorganic chemistry the term coordination entity is recommended instead of complex (IUPAC inorganic NOMENCLATURE (1990). See, http://www.chemicool.com/definition/complex.html.
(13) The definition of chelate: In reality, a chelate is any metal that is attached to an anion (negatively charged group) with more than one attachment site. Chelation means that the anion has two or more separate sites to which the metal is bonded. See, www.jostchemical.com.
(14) The definition of a dopant: a dopant is an impurity added usually in minute amounts to a pure substance to alter its properties. See, www.merriam-webster.com/dictionary/dopant. According to www.freedictionary.com, under medical the term to dope is used in materials sciences as a verb which means To add or incorporate a substance or other additive to a chemical compound of interest, with the intent of improving or altering performance parameters.
(15) The definition of fixed copper: a copper compound which is insoluble or highly insoluble in water. Fixed Coppers are further disclosed by H. Wayne Richardson in the Handbook Of Copper Compounds And Applications, page 97 third paragraph, suitable copper compounds include fixed coppers [Cu+(OH)2], Bordeaux, as well as other well known fixed copper compositions including those disclosed in CRV Handbook of Pest Management in Agriculture, Vol. 3, David Pimentel (editor), CRC Press, Boca Raton, Fla. (1981), which is incorporated herein by reference and Sabin '196 patent such as copper oxide/cuprous oxide, copper oxychloride, tribasic copper sulfate (CuSO.sub.4 3Cu(OH).sub.2, copper diammonia diacetate complex and/or any other well-known fixed or insoluble copper compositions currently being used, or has been prior used as a pesticide, fungicide, bactericide, and algaecide. Exemplary examples are copper hydroxide, copper/cuprous oxide, copper carbonate, copper oxychloride, basic carbonate, copper carbonate, basic copper sulfates including particularly tribasic copper sulfate, copper oxychlorides, and mixtures thereof, ammonia copper carbonate, basic copper chloride, and others, and mixtures thereof.
(16) The term iron doped copper hydroxide refers to a copper hydroxide compound that is doped with an iron compound. It is understood in alternate embodiments that the copper hydroxide compound may be substituted with another fixed copper compound as provided herein.
(17) The term zinc doped copper hydroxide refers to a copper hydroxide compound that is doped with a zinc compound. It is understood in alternate embodiments that the copper hydroxide compound may be substituted with another fixed copper compound as provided herein.
(18) The term zinc and iron doped copper hydroxide refers to a copper hydroxide compound that is doped with both an iron compound and a zinc compound. It is understood in alternate embodiments that the copper hydroxide compound may be substituted with another fixed copper compound as provided herein.
(19) Examples of iron compounds include any insoluble or substantially insoluble iron compound. Further examples include, but are not limited to iron compounds selected from the group consisting of iron hydroxide, iron oxyhydroxide, iron oxide, iron glucose, ferric citrate, Ferritin, ferrous fumarate, and ferrous sulfate. Most preferably the iron compound is iron hydroxide and/or iron oxyhydroxide.
(20) Examples of zinc compounds include any insoluble or substantially insoluble zinc compound. Further examples include, but are not limited to zinc compounds selected from the group consisting of zinc hydroxide and zinc oxide.
(21) In a preferred embodiment, the term insoluble or substantially insoluble is used herein. However, based on industry standards, Applicant submits that there is not a hard and fast quantitative definition for such terms as used by those of skill in the art. Accordingly, terms such as sparingly soluble, insoluble, highly insoluble, slightly soluble, (negligible) etc. have been used for decades by those of skill in the art. See, for Example U.S. Pat. No. 5,385,934, at column 1, lines 28-38, wherein Professor Emeritus Milton N. Schroth provides that These copper based compositions are typically aqueous fixed copper based compositions because the copper compounds used in these compositions typically have a solubility of free Cu+2 from about 1 to 30 ppm in the aqueous solution with the remainder (and the vast majority) of the copper either being insoluble or in chelated form (i.e., fixed). The 1 to 30 ppm of Cu+2 in such aqueous compositions is typically referred to as free copper to distinguish it from either the chelated Cu+2 or the insoluble Cu+2 in these fixed copper compositions. Similarly, Professor Santra discloses in U.S. Pat. No. 8,221,791 B1 An important consideration is whether to use soluble or insoluble copper(Cu) for long term fungicidal or bactericidal protection. The soluble Cu refers to Cu based salts (such as Cu sulphate) that hydrolyze completely in water, producing ionic Cu. The insoluble (sparingly soluble) Cu compounds act as a reservoir from which Cu ion is released to the plant surface on which it is deposited upon application. Additionally, Professor Santra provides Currently used Cu compounds possess unique set of physical and chemical properties. They differ in their total amount of metallic Cu content and aqueous solubility. It is well understood that the antibacterial activity will depend upon the availability of soluble (free and reactive) Cu ions in the formulation. Among the existing Cu compounds, tribasic Cu sulphates and cuprous oxide are least soluble, whereas Cu hydroxides are more soluble than Cu oxychloride. And Professor Santra further provides Several Cu compounds are registered in the United States for management of over 100 diseases on almost 50 food crops. The Cu compounds exhibit varying degrees of effectiveness for any target organism on any given host. The most common forms of Cu that satisfy these conditions to varying degrees are the normal hydrolysis products of Cu(1) and Cu(2) salts (also known as insoluble Cu of fixed Cu compounds: Cu(1) oxide, (Cu.sub.2O), Cu(2) oxychloride(CuCl.sub.2.3Cu(OH).sub.2), tribasic Cu(2) sulphate(CuSO.sub.43Cu(OH).sub.2, and Cu hydroxide(Cu(OH).sub.2. In Agrochemical and Pesticide Safety Handbook, Michael F Waxman discloses Since copper is toxic to plants, it must be used at low levels or in the insoluble form. For this reason, the relatively insoluble or fixed copper salts are used. These compounds release copper ions at very low rates that are adequate for fungicidal activity but not at concentrations that would harm or kill host plant. Richardson discloses Alternate products were developed primarily in the twenties and thirties and relied on low soluble or fixed coppers which could be applied as dusts or suspensions and A copper compound must be chosen that is relatively resistant to weathering and supplies enough copper to be toxic to the fungal spores and bacterial cells without adversely affecting the host. The most common forms of copper that satisfy these conditions to varying degrees are the normal hydrolysis products of copper(1) and copper(2) salts: copper (1) oxide(Cu2), cuprous oxide), copper(2) oxychloride(CuCl.sub.2.3Cu(OH).sub.2, tribasic copper(2)sulphate(CuSO.sub.4.3Cu(OH).sub.2, and copper hydroxides(Cu(OH).sub.2). These fixed coppers offer advantages of application and reduced phytotoxicity over the classic Bordeaux mixture. These are the terms Richardson uses: Pg 85, Copper(2) Phosphate Trihydrate, insoluble in cold water, Pg 55, Copper(1) Oxide, virtually insoluble in water Copper(2) oxide, Pp. 57,58, essentially insoluble in water, Pg 61, Copper(2)Hydroxide, virtually insoluble in water, Pg 63, Copper(2) carbonate Hydroxide, virtually insoluble in water, Pg 69, Copper(2) Oxychloride, essentially insoluble in water, Pg 79, Basic Copper(2) sulphate, insoluble in water, Pg 83, Copper(2)Gluconate, soluble in water. Richardson discloses a multitude of Copper compounds and descriptive nomenclature describing their solubility as above demonstrated.
(22) Those of the skill in the art can readily and easily test to determine the lower doses required of the applicant's invention to achieve disease control, and the doses to achieve disease control on copper resistant pathogens by standard routine testing.
(23) The iron doping of the copper hydroxide nanoparticles is from a trace contamination of iron, less than 0.01 at %, to about 40 at % iron with about 5-15 at % elemental iron preferred, with about 15 at % elemental iron the most preferred quantity. Other fixed coppers may incorporate more than 40 at % iron and/or zinc. While a variety of processes may be used to manufacture the doped component of the present invention, Applicant has used a wet chemical process as further indicated in detail below. It is understood to those of skill in the art that the process disclosed herein is scalable for commercial production. The product is dried/evaporated by methods well known to those skilled in the chemical art, and may be overcoated, if desired, with a stabilizer by methods well known to those in the chemical art. For example, See U.S. Pat. No. 4,404,169 to Ploss et al. entitled Process For Producing Cupric Hydroxide. The preferred size of an iron doped copper hydroxide nanoparticle is sub-micron, from about 0.5 nm to 30 microns. A more preferred size is from about 3.5 nm to 15 microns, an additional preferred size is from about 3.5 nm to 200 nm. A most preferred size is from about 3.5 nm to 10 nm, especially for both leaf protectorant and systemic activity all in one. Different sizes may be mixed together in the practice of the invention.
(24) Moreover, fixed copper compounds, such as copper hydroxide, are generally insoluble or highly insoluble in water. While not being limited, held or bound to any particular theory or mechanism of action, it is generally thought that The free copper penetrates into the bacterial and/or fungal micro-organism in order to exert its toxic effect. (See U.S. Pat. No. 5,202,353 of Schroth, Iron Enhancement of Copper Based Fungicidal and Bactericidal and Bactericidal Compositions, 1993). Applicant believes, in addition, that the generation of reactive oxygen species (ROS) by fixed copper compounds and the additional increase in ROS generation with the addition of an iron compound is pesticidal. Moreover, while not being limited held or bound of any particular theory or mechanism of action, it is thought that exudates on the surfaces of the plant leaves, taken together with the rainfall and the acidic rain, produce an acidic environment which dissolves the fixed copper compounds and releases free copper, which is very active against pathogens.
(25) Thus without being limited, held or bound to these plant diseases disclosed, there are hundreds and hundreds of plant diseases amenable to control by copper pesticides and that the applicants invention will surely potentiate the biocidal effects of copper pesticides against these pests. The composition of the present invention may be used with any known biologically inert carrier, including, but not limited to, a liquid diluent, e.g., water, a solid diluent and/or a surfactant. The composition of the present invention is designed to be compatible with the physical properties of copper hydroxide and any other active ingredients, method of application and environmental factors which may include soil type, moisture and temperature, organic matter, soil structure, current nutrient levels and more, well known to those in the chemical and agricultural art.
(26) Moreover, without being limited held or bound to any particular theory or mechanism of action, the more iron added to the copper hydroxide or other fixed copper, the more biocidal/robust pesticide the invention will be toward pests.
(27) Moreover, in one embodiment of the present invention herein, Applicant's iron doped copper hydroxide, or zinc doped copper hydroxide, or zinc and iron doped copper hydroxide, in an optional embodiment, may be stabilized or overcoated. U.S. Pat. No. 4,404,169 Ploss et al. discloses methods of stabilizing compounds of the applicant's invention. Overcoating, can modulate release of the active ingredient.
(28) In an alternate embodiment, insoluble iron compounds, such as iron hydroxide or iron oxyhydroxide, may be added to copper hydroxide so that there are two separate components. In a further alternate embodiment, iron hydroxide or other insoluble iron compounds, may be added to the iron doped copper hydroxide, so there are also two separate components. In each case, everything goes together in the spray tank for agricultural uses.
(29) Moreover, since iron and copper are recognized micronutrients, recognized by the American Society of Agronomy and the Soil Science Society of America, then it follows that the remaining micronutrients boron, chloride, manganese, molybdenum and zinc, can easily be added to the iron or zinc or iron and zinc doped copper hydroxide, which uses iron and or zinc as a dopant to produce a doped copper hydroxide iron fungicide/bactericide/nutrient with micronutrients for foliar, trunk, branch and/or root application and/or injection in the trunk or branches of the plant. Moreover, secondary nutrients such as calcium, magnesium and sulfur may also be added, singly or together in combination.
(30) Applicant's invention is the only known foliar nutritional bactericidal formulation that enters the phloem and kills the HLB disease causing CandidatusLiberibacter (CLas) bacteria.
(31) Since zinc has established anti-microbial activity against bacteria, fungi and other pathogens, Applicant proposes to potentiate, increase activity of the claimed iron doped copper hydroxide by further doping the copper hydroxide with a zinc compound so that the end product will be an iron doped, zinc doped copper hydroxide or other fixed copper. It is understood that the doping with zinc is provided by a zinc compound and not by the use of pure metallic zinc, an element.
(32) Preferred embodiments of this invention include both a zinc compound doped copper hydroxide and an iron compound doped copper hydroxide. Zinc sulfate is an exemplary example of a zinc salt thought to be useful in the manufacture of compounds of the invention. The sulfur in zinc sulfate is also a plant nutrient. Applicant also claims copper hydroxide which is both doped with an iron compound and a zinc compound together. In the preparation of the iron doped copper hydroxide, excess iron more than that the copper hydroxide will incorporate, is left in the preparation, so that the upshot is iron doped copper hydroxide, with additional iron hydroxide, in the preparation thereof. It may very well be an iron oxyhydroxide or other iron compound incorporated in the doping process.
(33) Iron doped copper hydroxide, with and without additional unincorporated iron hydroxide in the preparation, may be combined with zinc doped copper hydroxide with and without additional unincorporated zinc hydroxide or other zinc compounds, and both zinc and iron doped copper hydroxide with both additional unincorporated zinc and iron may also all be used in combinations or mixtures thereof.
(34) These combinations or mixtures thereof are easily tested against bacteria, fungi, viruses, mycoplasma and other pathogens, by rapid, well established, routine testing well known to those skilled in the art, such as laboratory high throughput screening of vast numbers of compounds in vitro, and/or greenhouse plantings.
(35) The compositions of the Applicant's invention are especially directed and exquisitely suited as a treatment for Huanglongbing (HLB) disease of citrus, and citrus canker, and other citrus diseases, such as Greasy Spot, Melanose, and Alternaria Brown Spot, where copper is currently utilized.
(36) Moreover, the small size of Applicant's invention will improve foliage coverage of leaves, which is well known in the art, that small particulates provide more uniform and superior coverage to leaves of plants. A critical and distinguishing feature of the Applicant's invention is that in preferred embodiments it can be an ultra-small insoluble copper and iron compound. Moreover, another critical aspect of Applicant's invention is the size of Applicant's iron doped copper hydroxide such that it is enabled for systemic uptake of the copper and iron. This size of Applicant's particles is unlike any size of any commercial fixed copper, so far as the Applicant is aware of, to facilitate systemic administration. Applicant's particulate at about 90+% particulate, is about 3.5 to 10 nm, as both a leaf protectorant and a systemic pesticide, and bactericide. Previous insoluble or fixed coppers are not systemic due to their large size for the most part. Applicant's particulate is about 90+% approximately 3.5 to 10 nm, in order to avoid aggregation, and has the best chance to facilitate systemic uptake. Preferably, Applicant's invention is to be administered with adjuvants/surfactants. Applicant's Transmission Electron Microscopy (TEM) image of
(37) In the foregoing description, certain terms and visual depictions are used to illustrate the preferred embodiment. However, no unnecessary limitations are to be construed by the terms used or illustrations depicted, beyond what is shown in the prior art, since the terms and illustrations are exemplary only, and are not meant to limit the scope of the present invention. Other fixed coppers may also be, joined, doped, with iron compounds and/or zinc compounds to practice the invention. Therefore, it is understood that Applicant's use of copper hydroxide for the fixed copper compound may be readily substituted with other known fixed copper compound. Copper hydroxide and other fixed coppers may be doped with insoluble iron compounds, and/or with insoluble zinc compounds.
(38) Moreover, because of the ultra-small size of the doped components in the Applicant's invention, at approximately 3.5-10 nm, it has been shown that copper hydroxide plus the adjuvant/superspreader Silwet-77 is toxic to the Asian Citrus Psyllid nymphs, a vector of bacterial HLB. Applicant's invention, with the addition of zinc (Zn) and iron (Fe), is thought to further enhance the pesticide efficacy of copper hydroxide or other fixed coppers against this vector/carrier of HLB bacteria, and adult vector/carrier Psyllid nymphs.
(39) The upshot is that doped components of the Applicant's invention hits the bacterial causes of HLB disease and XyellaFastidiosa infection of Olive Trees, and other external/internal plant pathogens in at least three ways at the least, as follows:
(40) a) as a leaf protectorant with supra fine particle size; i.e. 3.5-10 nm;
(41) b) as a leaf and systemic pesticide bactericide/fungicide; i.e. 3.5-10 nm; and,
(42) c) as a pesticide against vector/carrier of HLB bacteria, the Asian Citrus Psyllid nymphs
(43) and adults, and sharpshooters, froghoppers, and spittlebugs, vectors of XyellaFastidosa. Additionally, Applicant's invention simultaneously treats citrus canker and other citrus diseases.
(44) In one embodiment of the present invention, the doped component is a fixed copper compound doped with magnesium and/or calcium.
(45) Moreover, compounds of the Applicant's invention may be used with agents which currently synergizes with copper administration, such as for example Regalia biofungicide, and horticultural oils, and pesticidal adjuvants such as Silwet-L77, and other pesticides.
(46) Compounds of the present invention are suitable for the customary coatings, which include but not limited to surfactants, wetting agents, stabilizers, dispersants and anti-foam agents.
(47) Applicant claims iron compounds doped into copper hydroxide preferably iron hydroxide, zinc compounds doped into copper hydroxide preferably zinc hydroxide, iron compounds and zinc compounds doped together in copper hydroxide. These doped copper hydroxide compounds may be combined in any combination, or mixtures thereof and additional iron compounds, e.g. iron hydroxide, or zinc compounds, e.g zinc hydroxide, may be added. For example, iron hydroxide doped copper hydroxide at 15 at % iron may have free unincorporated iron hydroxide with it at 5, 10, 15, 20, 25, 30, 35 at % iron hydroxide or more together with the 15 at % iron hydroxide doped copper hydroxide. Applicant claims all fixed copper compounds doped with iron compounds and/or zinc compounds for agricultural pesticidal usage.
EXAMPLES
(48) The following examples illustrate the invention without limiting it. Except where otherwise indicated, the parts and percentages shown are expressed by percentage (at %).
Example 1
Synthesis of Iron-Doped Copper Hydroxide
(49) Iron-doped Copper Hydroxide (FeCu (OH).sub.2) composite powder is synthesized using a wet chemical process. The starting materials for the synthesis were copper nitrate hexahydrate(Cu(NO.sub.3).sub.2.6H.sub.2O), iron chloride (FeCl.sub.3), sodium hydroxide (NaOH) and deionized water (H.sub.2O). To synthesize 15 at % Fe-doped-Cu (OH).sub.2, 2.43 g of copper nitrate hexahydrate and 0.4 g of iron chloride were dissolved in 75 mL of deionized water in a round bottom flask. The solution was refluxed for 3 hours. Once the solution cooled down to room temperature, 102.2 mL of 0.25 M NaOH was added. The pH at this stage was between 10 and 11. Subsequently, the solution was transferred to a beaker and another 102.2 mL of NaOH was added, while stirring the solution, using a high shear mixer at 1000 rpm. The pH after the addition of NaOH was between 11 and 12. The precipitate was washed one time using deionized water and finally dried in air. Similar methods were used to synthesize iron-copper hydroxide composite, where the amount of iron was varied from 20 to 50 at %.
(50)
Example 2
Synthesis of Iron-Zinc-Doped Copper Hydroxide
(51) Iron-Zinc-doped Copper Hydroxide (FeZnCu (OH).sub.2) composite powder is synthesized using a wet chemical process. The starting materials for the synthesis is copper nitrate hexahydrate (Cu (NO.sub.3).sub.2.6H.sub.2O), iron chloride (FeCl.sub.3), zinc sulfate heptahydrate (ZnSO.sub.4.7H.sub.2O), sodium hydroxide (NaOH) and deionized water (H.sub.2O). To synthesize 7.5 at % Fe 7.5 at % Zn-doped-Cu(OH).sub.2, 2.43 g of copper nitrate hexahydrate, 0.21 g of zinc sulfate heptahydrate and 0.19 g of iron chloride is dissolved in 75 mL of deionized water in a round bottom flask. The solution is refluxed for 3 hours. Once the solution cools down to room temperature, 102.2 mL of 0.25 M NaOH is added. Subsequently, the solution is transferred to a beaker and another 102.2 mL of NaOH is added, while stirring the solution, using a high shear mixer at 1000 rpm. The precipitate is washed one time using deionized water and finally dried in air. The similar method is used to synthesize other variations of iron-zinc-copper hydroxide composite.
Example 3
Synthesis of Zinc-Doped Copper Hydroxide
(52) Zinc-doped Copper Hydroxide (ZnCu(OH).sub.2) composite powder is synthesized using a wet chemical process. The starting materials for the synthesis is copper nitrate hexahydrate (Cu(NO.sub.3).sub.2.6H.sub.2O), zinc sulfate heptahydrate (ZnSO.sub.4.7H.sub.2O), sodium hydroxide (NaOH) and deionized water (H.sub.2O). To synthesize 15 at % Zn-doped-Cu(OH).sub.2, 2.43 g of copper nitrate hexahydrate, 0.42 g of zinc sulfate heptahydrate is dissolved in 75 mL of deionized water in a round bottom flask. The solution is refluxed for 3 hours. Once the solution cools down to room temperature, 102.2 mL of 0.25 M NaOH is added. Subsequently, the solution is transferred to a beaker and another 102.2 mL of NaOH is added, while stirring the solution, using a high shear mixer at 1000 rpm. The precipitate is washed one time using deionized water and finally is dried in air. The similar method is used to synthesize other variations of zinc-copper hydroxide composite.
(53) Although the present invention has been disclosed in terms of a preferred embodiment, it is further known that other modifications may be made to the present invention, without departing from the spirit and scope of the invention.