WO2017131958A1 - Potentiation of fixed coppers and other pesticides - Google Patents
Potentiation of fixed coppers and other pesticides Download PDFInfo
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- WO2017131958A1 WO2017131958A1 PCT/US2017/013113 US2017013113W WO2017131958A1 WO 2017131958 A1 WO2017131958 A1 WO 2017131958A1 US 2017013113 W US2017013113 W US 2017013113W WO 2017131958 A1 WO2017131958 A1 WO 2017131958A1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
Definitions
- the present invention relates to potentiation of pesticides containing fixed copper in human, agricultural, fungicidal, bactericidal, anti-pathogen and biocidal applications, by increasing the activity of its biocidal effects, so that less polluting copper is used.
- Xylella infection is a bacterium, which inhabits the internal vascular compartment of the olive tree, the xylem, and causes like HLB, plants to dry out, die, leaving shriveled stumps, that are incapable of bearing fruit. See also the Daily Mail, in the published article at "Olive Oil Under Threat From Bacteria Which Is Hitting H undreds Of Thousands Of Trees In Italy— And could Set prices Soaring" by Hannah Roberts, and "Italian Government Urged To Take Action To Fight against Olive Tree Epidemic" in Agro News, January 9, 2015, Like HLB, there are few treatments which target the internal vascular system of olive trees,
- HLB disease of citrus is a devastating phloem limited incurable bacterial infection which is decimating/killing the citrus industry worldwide.
- Novel Bactericides and Application Methods to Control Huanglongbing Disease of Citrus which discusses an overview of "inconsequential effect of nutritional treatments on Huanglongbing control, fruit quality, bacterial titer and disease progress" by T.R. Gottwald, J.H. Graham, et al.
- compositions Tim Spann, which discloses “every fertilizer manufacturer now produces their own program of foliar nutrition for HLB.” Further disclosed is the “Maury Boyd cocktail”, which is the original nutritional foliar spray for HLB disease support.
- Copper (II) hydroxide also known as cupric hydroxide and having the chemical formula Cu(OH) 2
- Cu(OH) 2 Copper (II) hydroxide
- 2,525,242, 2,536,096 and 3,635,668 disclose processes involving ammonia.
- the processes of U.S. Patent Numbers 2,525,242 and 2,536,096 involve oxidation of copper metal in the presence of ammonia and U.S. Patent Number 4,944,935 discloses a similar process substituting ammonium ion for all or part of the ammonia.
- the other proce ses start with a soluble copper salt, typically copper (II) sulfate.
- U.S. Patent Number 4,404,169, European Patent Number EP 80226 BI and PCT Patent Publication WO 02/083566 A2 describe processes starting with copper (II) oxychloride. J.
- Nufarm discloses the history of copper fungicides, the history of copper hydroxide, how copper hydroxide works, how copper works, particle size of copper hydroxide fungicide and more information, including about their products Champ® Dry Prill, Champ® Formula 2 Flowable and Champion® WP (See Nufarm Americas Inc., Nufarm Agriculture Division, "The Copper Champs! ⁇ 2002.)
- DuPont discloses a similar product, DuPont Kocide Blue Xtra with similar information.
- DuPont discloses a bewildering array of dozens of plant diseases, treated with DuPontTM Kocide® 3000 Fungi ci de/B acteri ci de, on a multitude of agricultural crops.
- Copper pesticides, fungicides, and bactericides are extremely toxic to fish, and aquatic organisms. (Nufarm Americas Inc., Agt Division, Champ® WG Specimen Label). Runoff from the use of copper fungicides, bactericides and algaecides into waterways, ground water and the ground is a very serious contamination problem well known to those in the art.
- U.S. Patent Number 5,202,353 of Schroth, Iron Enhancement of Copper Based Fungicidal and Bactericidal and Bactericidal Compositions 1993, discloses that the addition of soluble iron to copper hydroxide fungicide increases activity of the copper hydroxide fungicide bactericide and reverses resistance to copper in vitro.
- U.S. Patent Number 5,385,934 of Schroth, Methods for Preventing Precipitation of Copper Based Bactericidal Compositions Containing Iron discloses the addition of an aggregation inhibiting salt to the copper plus iron compositions to prevent aggregate/or sediment formation upon the addition of Fe+3 to the composition.
- Zinc-doped CuO nanocomposites of a specific size are known for use in specific fields.
- Eyal Malka et al., (small 2013, DOl:10.i002/s:mll.201301081, www.small- joumal.com) discloses, "eradication of multi-drug resistant bacteria by a novel zinc-doped CuO n ano composite.”
- Michal Eshed, et al., (Advanced Functional Materials 2014, pp.1382-1390, www.afm-journal.de) discloses, "a Zn-doped CuO nanooomposite shows enhanced anti-bio film and antibacterial activities against Streptococcus mutans compared to nanosized CuO.” They conclude, "the results of the present study further highlight the potential of these novel Zn:CuO np's as inhibitors of biofilm within the context of the oral niche.”
- Richardson provides, "commercially produced cupric oxide (copper(2) oxide) is ineffective as a fungicide or bacter
- Ploss, et al, United States Patent 7,1.05,1 6 B2 discloses that doping 5 wt % zinc metal, into a copper salt composition intended for agricultural applications provided enhanced surface adhesion, as in the case of plants on leaf and fruit surfaces, thereby increasing the duration of the plant-protecting effects and also eliminating the expense and environmental emissions associated with the re-application of prior art compositions that would be required to provide the same level of protection.
- Floss's use of metallic zinc to provide enhanced surface adhesion does not teach any ad vantages with regard to pesticidal characteristics per se.
- zinc is a metal, an element and is insoluble in water, with a small surface area.
- Nufarm's Spraymate bond is a high quality sticker, deposition and retention agent for use with contact or protectant type fungicides or with contact and ingested insecticides. Spraymate bond increases adherence of spray droplets by sticking them firmly to target surfaces.
- Spraymate bond also protects chemicals by slowing the rate of degradation immediately after application. Its key benefits are that it improves spray droplet deposition, retains and protects droplets on targets, improves the performance and life of protectant fungicides and contact insecticides. Furthermore, there is a world of difference between pure zinc metal, an element, and insoluble pesticidal zinc compounds.
- This invention is directed to a pesticide, fungicidal, bactericidal, anti-pathogen or biocidal composition
- a pesticide, fungicidal, bactericidal, anti-pathogen or biocidal composition including a) at least one biologically inert carrier and; b) at least one doped component comprising at least one fixed copper compound, such as copper hydroxide, doped with at least one compound selected from the group consisting of iron compounds, zinc compounds, magnesium compounds, calcium compounds, and combinations tliereof.
- the doped component only includes iron compounds and/or zinc compounds as the only doping compounds.
- the doped component has a particle size of about 0.5 run to 30 microns.
- the iron compound and/or zinc compound are doped into the fixed copper compound, such as copper hydroxide, singly or together in combination.
- a fixed copper compound is doped with an insoluble iron compound, such as, for example, where the fixed copper compound, is copper hydroxide, and wherein the fixed copper compound is partially substituted by an insoluble iron compound.
- a surfactant may be included in the composition to provide for a more efficacious formulation.
- the composition includes doped components that contain both the fixed copper compounds and the iron, zinc, magnesium, and/or calcium compounds combined on the doped component.
- the fixed copper compound such as copper hydroxide
- doped with the iron compound and/or zinc compound is used in order to provide a more cost effective composition with increased activity as compared to copper hydroxide alone. Therefore, less copper is required, with its resultant reduced runoff, and less pollution derived from copper.
- iron is a plant micronutrient and the present composition would supply iron to plants as against copper hydroxide alone. It has been found that: heavy use of copper compounds produces iron chlorosis.
- copper hydroxide is a pesticide, rungicide/bactericide that is so well established so that the present invention could be administered very similarly to the current methods of copper hydroxide administration with a straight substitution, more or less, except that the amount of elemental copper derived from the present invention will be reduced, as against stand-alone copper hydroxide, to achieve the same or greater control or pathogen reduction.
- Appli cant submits that the present invention may be substi tuted for the copper hydroxide in PCT Patent
- Applicant's present invention may be provided as a pesticide, fungicide, bactericide, anti-pathogen and biocidal nutrient spray with optional additional micronutrients and/or optionally macronutrients, so tiiat there would be a combination copper based pesticide with micronutrients all in one formulation.
- Applicant's present invention includes an insoluble copper pesticide, fungicide, bactericide, and anti-pathogen and biocidal capable of systemic uptake by foliar, root and/or trunk injection, and a plant protectorant, dual mode of action, all in one compound.
- the prior art teach es various complexes of copper compounds, mixtures which are two or more substances that are not chemically combined, and chelates of copper compounds.
- Compounds of the present invention are overwhelmingly, compellingly, and persuasively, distinguishable, as doped zinc compounds and doped iron compounds are internalized in the copper hydroxide or other fixed coppers. Complexes and chelates are joined so that they are externalized to the copper hydroxide or other fixed coppers.
- Applicant's doped components can also be sized at about 5nni-10nm, and other larger particulates, in one embodiment, to provide both plant protectorant and systemic uptake to be carried internally through the plant phloem and xylem to kill systemic bacterial infections such as HLB, and Xylcllafastidosa. and other systemic pathogenic fungi, or internal pathogens.
- Applicant's doped composition of fixed coppers doped with zinc, iron, or both, are also useful in treating banana plants afflicted with the Sigatoka complex of banana fungal diseases, including Black Sigatoka disease, Yellow Sigatoka disease, and eumusae leaf spot disease, as well as also Panama disease.
- the composition is useful in treating banana fungal diseases such as, for example, but not limited to, Black Sigatoka disease, Yellow Sigatoka disease, leaf spot Sigatoka disease, Panama disease, Fusarium wilt, Antliracnose, Armillaria corn rot, Black cross, Black root rot, Brown blotch, Brown spot, Ceratocystis fruit rot, Cigar-end, Cladosporium speckle, Conn, dry rot, Crown rot.
- banana fungal diseases such as, for example, but not limited to, Black Sigatoka disease, Yellow Sigatoka disease, leaf spot Sigatoka disease, Panama disease, Fusarium wilt, Antliracnose, Armillaria corn rot, Black cross, Black root rot, Brown blotch, Brown spot, Ceratocystis fruit rot, Cigar-end, Cladosporium speckle, Conn, dry rot, Crown rot.
- Cylindrocladium root rot Damping-off disease, Deightoniella fruit speckle, Diamond spot, Dwarf Cavendish tip rot, Eyespot, Fruit freckle, Fruit rot, Fungal fruit rot, Leaf rust, Leaf speckle, Main Stark rot, Malayan leaf spot, Marasmiellus rot, Peduncle rot, Pestalotiopsis leaf spot, Phaeoseptoria leaf spot, Pitting disease,
- composition is also useful for treating bacterial diseases of banana plants, , such as, for example, but not limited to, Xanthomonas wilt, Banana bacterial wilt, Enset wilt, Blood disease, Bugtok disease, gumming finger tip rot, Moko disease, Rhizome rot, and Japanese vascular wilt disease.
- composition is also useful for treating viral diseases in banana plants, such as, for example, but not limited to, Bract mosaic disease, Banana bunchy top disease, Abaca mosaic disease, Banana streali virus disease, Badnavirus, viral caused chlorosis, Cigar leaf necrosis, cucumber mosaic virus, Sugarcane bacilliform virus, and banana virus X disease.
- viral diseases in banana plants such as, for example, but not limited to, Bract mosaic disease, Banana bunchy top disease, Abaca mosaic disease, Banana streali virus disease, Badnavirus, viral caused chlorosis, Cigar leaf necrosis, cucumber mosaic virus, Sugarcane bacilliform virus, and banana virus X disease.
- Applicant's invention clearly will not displace and replace the entire world use of pesticides. However, applicant's invention will clearly replace and displace many of the highly toxic pesticides currently being used against pests which are resistant to existing copper pesti cides .
- Applicant's invention will decrease the breadth, depth and range of pesticides currently resistant to copper pesticides, restoring sensitivity and high activity. Moreover a Google search discloses over 52 million hits for the well-known established harmful effects of pesticides.
- FIG. 1 is a copy of an X-Ray Diffraction test showing copper hydroxide doped with. 1 at% insoluble iron as a dopant in accordance with one embodiment of the present invention. There are no additional peaks proving that the iron is incorporated within the copper hydroxide.
- FIG. 2 is a transmission electron microscopy (TEM) image of Applicant's iron doped copper hydroxide at 15 at% iron in accordance with one embodiment of the present invention.
- the scale on the lower left of FIG. 2 shows a comparable length of 50 nm.
- the size of the iron doped 15 at% Fe copper hydroxide particulates is about 3.5 nm to 9 nm, tested in quadruplicate and by transmission electron microscopy (TEM).
- FIG.3 is an elemental analysis chart demonstrating the presence of both iron and copper in the iron doped copper hydroxide compound in accordance with one embodiment of the present invention of FIG, 1 and FIG. 2 above.
- FIG. 4 is the X-ray diffraction of 15 at% iron doped copper hydroxide with an additional 10 at% iron that the copper hydroxide is unable to incorporate, so that the final composition is 15 at% iron doped copper hydroxide + 10 at% unincorporated/free iron hydroxide and/or iron oxide.
- the invention is a pesticide, fungicidal, bactericidal, anti-pathogen or biocidal composition
- 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.
- the doped component only includes iron compounds and/or zinc compounds as the only doping compound.
- copper hydroxide may be doped with iron hydroxide, iron oxyhydroxide or other iron compound as one doped component.
- 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.
- the fixed copper compound such as copper hydroxide
- 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.
- 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.
- copper hydroxide is doped with iron hydroxide to provide 15at% iron to the doped component, which results in a black doped component.
- the atomic percentage (at%) of iron in the doped component is less than 15 at %, more preferably less than 10 at%.
- 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 acti vity 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.
- doped compositions cannot be separated by physical means. The dopant is incorporated within the structure of the compounds of interest, and becomes part of it.
- Haldolaarachchige, et al "Effect of Chemical Doping on the Thermoelectric Properties of Fe Gaz," Journal of Applied Physics, March 2011 , describes that doping increases carrier density and results in a new metallic state.
- Haldolaarachchige, et al. also disclose the preparation of the chemically doped FeGaz doped with either Co or Ge.
- Haldolaarachchige, et al. states in "IV. Conclusions” as follows: "Even small amounts of chemical doping have a significant effect on the physical properties and electronic structure of the pure compound.”
- 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.
- Pests are 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.”
- Mixtures contain 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 fdtration and distillation. Mixtures have variable compositions while compounds have a fixed definite formula.
- NORDQX 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.
- Elements and compounds are pure chemical substances found in nature. The difference between an element and a compound is that an el ement 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 2 0) and salt (sodium chloride-NaCl)." See,
- 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://3 ⁇ 4ww.ehemicool.conVdefinition/complex.hrml.
- 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.' 1 See,
- 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.freedictionaiy.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. "
- 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 tliird 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.
- 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 oxychloricles, and mixtures thereof, ammonia copper carbonate, basic copper chloride, and others, and mixtures thereof.
- 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.
- 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.
- 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.
- 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 firmarate, and ferrous sulfate. Most preferably the iron compound is iron hydroxide and/or iron oxyhydroxide.
- 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.
- insoluble or substantially insoluble is used herein.
- Applicant submits that there is not a hard and fast quantitative definition for such terms as used by those of skill in the art.
- 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.”
- 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.”
- the iron doping of the copper hydroxide nanoparticles is from a trace
- the preferred size of an iron doped copper hydroxide nanoparticle is sub-micron, from about 0.5nm to 30 microns. A more preferred size is from about 3.5nm to 15 microns, an additional preferred size is from about 3.5nm to 200nm. A most preferred size is from about 3.5nm to lO m, especially for both leaf pro tectorant and systemic activity all in one. Different sizes may be mixed together in the practice of the invention.
- fixed copper compounds such as copper hydroxide
- ROS reactive oxygen species
- 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 diluen t and/or a surfactant.
- a liquid diluent e.g., water, a solid diluen t and/or a surfactant.
- composition of the present invention is designed to be compatible with the physical properties of copper hydroxide and any other active ingredients, metliod 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.
- 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.
- United States Patent 4,404,169 PIoss, et al. discloses methods of stabilizing compounds of the applicant's invention. Overcoating, can modulate release of the active ingredient.
- insoluble iron compounds such as iron hydroxide or iron oxyhydroxide
- copper hydroxide may be added to copper hydroxide so that there are two separate components.
- 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, evciything goes together in the spray tank for agricultural uses.
- 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 fungicide bactericide/nutrient with micronutrients for foliar, trunk, branch and/or root application and/or injection in the trunk or branches of the plant.
- secondary nutrients such as calcium, magnesium and sulfur may also be added, singly or together in combination,
- Applicant's invention is the only known foliar nutritional bactericidal formulation that enters the phloem, and kills the HLB disease causing CandidatusLiberibacter (CLas) bacteria.
- Applicant proposes to potentiate, increase activity of the cl aimed 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.
- 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.
- 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.
- Other useful compounds are ferrites, which may be an additional alternate compound to be used stand alone, or may be combined as the iron and/or zinc doped copper hydroxide is also used.
- a ferrite is a type of ceramic compound composed of iron oxide combined with one or additional metallic elements in chemical combination. See Encyclopedia Britannica. See Wikipedia. Exemplary examples are copper zinc iron oxide (CuZnFe 2 .04).
- tine size of the ferrites are from 0.5 nm up to 30 microns.
- compositions of the Applicant's invention are especially directed and extraordinarly 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.
- Applicant's doped composition of fixed coppers doped with zinc, iron, or both are also useful in treating banana plants afflicted with Black Sigatoka disease, Yellow Sigatoka disease and Panama disease.
- Applicant's invention is that in preferred embodiments it can be an ultra-small insoluble copper and iron compound.
- 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 1 Onm, as both a leaf pro tectorant and a systemic pesticide, and bactericide.
- 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.
- Applicant's invention is to be administered with adjuvants/surfactants.
- Adjuvants ma be one or more metal chelates preferably an iron chelate.
- Applicant's Transmission Electron Microscopy (TEM) image of F1G.2 herein was tested with a surfactant, to insure good separation.
- Typical surfactants thought to be useful for the Applicant's invention are described in Silwet Adjuvants and SAG Antifoams for Agricultural Applications, (2012), published in Momentive publication of Momentive Performance Materials, Inc. of Albany, NY and "Adjuvants Products Guide” of Nufarrn.
- Applicant's invention at approximately 3.5-lOnm, 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
- the upshot is that doped components of the Applicant's invention hits the bacterial causes of HLB disease and yella fastidiosa infection of Olive Trees, and other external/internal plant pathogens in at least three ways at the least, as follows:
- Applicant's invention simultaneously treats citrus canker and other citrus diseases.
- the d oped component is a fixed copper compound doped with magnesium and/or calcium.
- compounds of the Applicant's invention may be used with agents which currently synergizes with copper administ-ation, such as for example Regalia biofungicide, and horticultural oils, and pesticidal adjuvants such as Silwet-L77, and other pesticides.
- agents which currently synergizes with copper administ-ation such as for example Regalia biofungicide, and horticultural oils, and pesticidal adjuvants such as Silwet-L77, and other pesticides.
- Compounds of the present invention are suitable for the customary adjuvants, such as metal chelates, preferably at least one iron chelate, and formulation aids, which include but not limited to surfactants, wetting agents, stabilizers, dispersants and anti-foam agents.
- metal chelates preferably at least one iron chelate
- formulation aids which include but not limited to surfactants, wetting agents, stabilizers, dispersants and anti-foam agents.
- These doped copper hydroxide compounds may be combined i any combination, or mixtures thereof and additional iron compounds, e.g. iron hydroxide, or zinc compounds, e.g. zinc oxide, may be added.
- 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.
- Iron-doped Copper Hydroxide (Fe-Cu (OH) 2 ) composite powder is synthesized using a wet chemical process.
- the starting materials for the synthesis were copper nitrate hexahydrat e(Cu(>l 0 ;i h .6H 2 0), iron, chloride (FcCL), sodium hydroxide (NaOH) and deionized water (H 2 Q).
- To synthesize ⁇ 15 at% Fe-doped- Cu ( ⁇ ) 2 2.43g 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 reiluxed for 3 hours.
- FIG. 1 is an X-ray diffraction test verifying that copper hydroxide is doped with an insoluble iron.
- Applicant submits a data sheet of Applicant's iron doped copper hydroxide with 15 at% iron elemental analysis of FIG.3.
- FIG. 2 discloses Applicant's invention tested out by TEM at about 90%+ particulates, which is a very narrow particulate distribution unlike any other commercial product, between 3.5nm and lOnm.
- Fig.4 is the X-ray diffraction of 15 at% Iron doped+ additional 10 at% iron that the copper hydroxide is unable to incorporate, so that the final preparation i s 15 at% Iron doped copper hydroxide+ 10 at% unincorporated/free Iron Hydroxide and or Iron Oxide.
- Iron-Zinc-doped Copper Hydroxide (Fe-Zn-Cu (OH) 2 ) composite powder is synthesized using a wet chemical process.
- the starting materials for the synthesis is copper nitrate hexahydrate (Cu (N0 3 ) 2 .6H 2 0), iron chloride (FeCI 3 ), zinc sulfate heptahydrate (ZnS0 4 .7H 2 0), sodium hydroxide (NaOH) and deionized water (H 2 0).
- Zinc-doped Copper Hydroxide (Zn-Cu(OH) 2 ) composite powder is synthesized using a wet chemical- process.
- the starting materials for the synthesis is copper nitrate hexahydrate ( ⁇ ( ⁇ 0 3 ) 2 . ⁇ 2 ⁇ ), zinc sulfate heptahydrate (ZnS0 4 .7H 2 0), sodium hydroxide (NaOH) and deionized water (3 ⁇ 40),
- To synthesize ⁇ 15 at% Zn-doped- Cu(OH) 2 2.43g 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 stimng 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.
- the Applicant preferably has used additional zinc sulfate heptahydrate, so that the finished synthesis contains zinc doped copper hydroxide plus unincorporated zinc oxide alone, in the finished preparation.
- the Applicant's agricultural pesticides used to treat agricultural crops affected, with vascular crop diseases such as Huang-longbing bacterial disease in orange crop plants or Xylella fasfidosa disease in olive tree crop plants, namely with zinc or iron -doped copper hydroxide singly or together, and/or with ferrites, are extraordinarly also suited for fungal diseases of banana, especially the three leading banana killers worldwide, namely Black Sigatoka disease, Yellow Sigatoka disease and Panama disease.
- the present invention is also useful against other banana fungal diseases, including eumusae leaf spot disease, which is also of the Sigatoka complex of banana fungal diseases,
- Bananas are a. staple for an. excess of 400 million subsistence people in the tropics. They are under vicious critical attack by these fungal diseases. See Mourichon et al, Sigatoka Leaf Spot Diseases, PROMUSA Working Group, International Network for Improvement of Banana and Plantai n Jardin Cedex, FR,
- Ramaker "Banana disease continues to Spread", resource.wageningenur.nl, November 26, 2015, showing aerial photos depicting widespread destruction of banana plants in a banana plantation.
- Ramaker states that there is widespread destru ction, of banana plants in. the Middle East, Southeast Asia, East Africa and Australia affected by Panana disease of banana plants, Ramaker also states it is only a matter of time before it spreads to South America.
- Ramaker notes that efforts to quarantine afflicted banana plants have failed to stop the spread of Panama disease in banana plants..
- Ramaker notes that: the Panana disease causing fungus Fusarium o sorum survives in the soil for long periods of time, even after afflicted banana plants are removed.
- Applicant's invention In contrast to known fungicides, Applicant's invention with its preferred 5-1 Onm size will enter the banana leaf through the stoma, or by other means, which, is referred to being "locally systemic", to counter the fungus systemically affecting the afflicted banana plant. Simultaneously, the compositions of Applicant's invention act like other classical fixed coppers, as a crop protectant on the surface of the leaf. Moreover, the compositions of Applicant's invention is used to reduce the number of sprayings due to wet weather, because of its systemic activity like the prior systemics, which were unsuccessfully used to try and control Black Sigatoka disease or Yellow Sigatoka disease in banana plants.
- Etebu states as follows: "Protectants were the first group of fungicides that were discovered and. used in crop protection. They are non systemic, and as such do not penetrate plant tissue. Protectant fungicides do not control fungi that are already established within the plant tissues since they do not penetrate the plant tissues themselves. "
- the Applicant's fungicidal compositions are distinguished from the prior art by their unique doping with zinc and/or iron, singly or together, and with a unique small size, capable of entering the banana plant leaf, the site of infection.
- Panama disease s another blight affecting afflicted banana plants.
- Panama disease is caused by a fungus Fusarium oxysporum f.sp. cubense (Foe), which, along with Black Sigatoka are the two grievous existential threats to banana crop production and the lifeblood of over 400 million subsistence banana crop fanners.
- Panama disease is a vascular fungus which can remain active in the soil for many decades and it cannot be fully controlled by prior art fungicides. There is a desperate need for treatment for Panama disease. See “YES WE HAVE NO BANANAS: The world's favorite fruit is slowly but surely being driven to extinction" by Gwynn Guilford in Quartz; See also "Yes! We have no bananas?
- Applicant's fungicidal compositions with their small size suitable for systemic uptake, in the banana plant, and the proven anti-fungal characteristics of the fixed coppers i.e. copper hydroxide, plus being doping with iron and/or zinc, make Applicant's compositions very desirable for the treatment of Panama disease.
- the present invention for treating banana fungal, bacterial and viral diseases includes a pesticidal, fungicidal, bactericidal, anti-pathogen or biocidal composition for use in the treatment of fungal, bacterial and viral diseases of banana plants wherei the composition comprises
- At least one doped component comprises 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, or,
- At least one doped component comprises 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.
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- Inorganic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
Description
Claims
Priority Applications (3)
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BR112018014956A BR112018014956A2 (en) | 2016-01-25 | 2017-01-12 | potentiation of fixed coppers and other pesticides |
CN201780019224.9A CN109068633A (en) | 2016-01-25 | 2017-01-12 | The enhancing of fixed copper and other pesticides |
PH12018501581A PH12018501581A1 (en) | 2016-01-25 | 2018-07-25 | Potentiation of fixed coppers and other pesticides |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
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US15/005,988 US9487453B2 (en) | 2014-05-23 | 2016-01-25 | Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition |
US15/005,988 | 2016-01-25 | ||
US15/005,969 | 2016-01-25 | ||
US15/005,969 US9586871B2 (en) | 2014-05-23 | 2016-01-25 | Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition |
US15/343,032 US9854807B2 (en) | 2014-05-23 | 2016-11-03 | Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition |
US15/343,032 | 2016-11-03 | ||
US15/343,004 | 2016-11-03 | ||
US15/343,004 US20170050893A1 (en) | 2014-05-23 | 2016-11-03 | Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition |
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WO2017131958A1 true WO2017131958A1 (en) | 2017-08-03 |
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PCT/US2017/013113 WO2017131958A1 (en) | 2016-01-25 | 2017-01-12 | Potentiation of fixed coppers and other pesticides |
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CN (1) | CN109068633A (en) |
BR (1) | BR112018014956A2 (en) |
EC (1) | ECSP18056182A (en) |
PH (1) | PH12018501581A1 (en) |
WO (1) | WO2017131958A1 (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5202353A (en) * | 1991-01-22 | 1993-04-13 | The Regents Of The University Of California | Iron enhancement of copper based fungicidal and bactericidal compositions |
US6720313B1 (en) * | 1998-04-17 | 2004-04-13 | Mattersmiths Holdings Limited | Biocidal composition containing phosphite ions |
US20060276339A1 (en) * | 2002-10-16 | 2006-12-07 | Windsor J B | Methods and compositions for increasing the efficacy of biologically-active ingredients |
US20070248673A1 (en) * | 2006-04-25 | 2007-10-25 | Martinez Alfonso G | Copper-based fungicide/bactericide |
US20110052720A1 (en) * | 2007-12-20 | 2011-03-03 | Wim Van Der Krieken | Compositions for the control of plant pathogens and for use as plant fertilizer |
US20140023691A1 (en) * | 2011-03-25 | 2014-01-23 | North Carolina State University | Inhibition of bacterial biofilms and microbial growth with imidazole derivatives |
WO2015179478A1 (en) * | 2014-05-23 | 2015-11-26 | Robert Sabin | Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition |
-
2017
- 2017-01-12 WO PCT/US2017/013113 patent/WO2017131958A1/en active Application Filing
- 2017-01-12 BR BR112018014956A patent/BR112018014956A2/en not_active Application Discontinuation
- 2017-01-12 CN CN201780019224.9A patent/CN109068633A/en active Pending
-
2018
- 2018-07-25 EC ECSENADI201856182A patent/ECSP18056182A/en unknown
- 2018-07-25 PH PH12018501581A patent/PH12018501581A1/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5202353A (en) * | 1991-01-22 | 1993-04-13 | The Regents Of The University Of California | Iron enhancement of copper based fungicidal and bactericidal compositions |
US6720313B1 (en) * | 1998-04-17 | 2004-04-13 | Mattersmiths Holdings Limited | Biocidal composition containing phosphite ions |
US20060276339A1 (en) * | 2002-10-16 | 2006-12-07 | Windsor J B | Methods and compositions for increasing the efficacy of biologically-active ingredients |
US20070248673A1 (en) * | 2006-04-25 | 2007-10-25 | Martinez Alfonso G | Copper-based fungicide/bactericide |
US20110052720A1 (en) * | 2007-12-20 | 2011-03-03 | Wim Van Der Krieken | Compositions for the control of plant pathogens and for use as plant fertilizer |
US20140023691A1 (en) * | 2011-03-25 | 2014-01-23 | North Carolina State University | Inhibition of bacterial biofilms and microbial growth with imidazole derivatives |
WO2015179478A1 (en) * | 2014-05-23 | 2015-11-26 | Robert Sabin | Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition |
Also Published As
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ECSP18056182A (en) | 2018-10-31 |
PH12018501581A1 (en) | 2019-04-08 |
BR112018014956A2 (en) | 2018-12-26 |
CN109068633A (en) | 2018-12-21 |
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