GB2614742A - Pesticidal composition - Google Patents

Pesticidal composition Download PDF

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Publication number
GB2614742A
GB2614742A GB2200542.5A GB202200542A GB2614742A GB 2614742 A GB2614742 A GB 2614742A GB 202200542 A GB202200542 A GB 202200542A GB 2614742 A GB2614742 A GB 2614742A
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Prior art keywords
pesticidal composition
potassium
lactoferrin
sodium
plants
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GB2200542.5A
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Moore-Smith Marc
Jack Rose Samuel
Jones Karen
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Acromore Ip Ltd
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Acromore Ip Ltd
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Priority to GB2200542.5A priority Critical patent/GB2614742A/en
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N63/00Biocides, pest repellants or attractants, or plant growth regulators containing microorganisms, viruses, microbial fungi, animals or substances produced by, or obtained from, microorganisms, viruses, microbial fungi or animals, e.g. enzymes or fermentates
    • A01N63/50Isolated enzymes; Isolated proteins
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00Disinfectants; Antimicrobial compounds or mixtures thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00Fungicides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07KPEPTIDES
    • C07K14/00Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/435Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
    • C07K14/79Transferrins, e.g. lactoferrins, ovotransferrins

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Microbiology (AREA)
  • Virology (AREA)
  • Biotechnology (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Mycology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

A pesticidal composition for controlling and/or preventing disease in a plant, the pesticidal composition comprises lactoferrin, an aqueous base, and optionally one or more of an antifoaming agent, a preservative, a non-ionic surfactant, a soil conditioner and an acidity regulator. Lactoferrin may be present in up to 8 weight per cent, e.g., 0.005 – 7.5 wt.%. The aqueous base may be more than 95 % water. The pesticidal composition may be up to 99 % aqueous base. The antifoaming agent may comprise a silicone and may be present at 0.02 – 0.06 weight% of the pesticidal composition. The preservative may account for 0.1 – 0.3 wt.% of the composition. The soil conditioner may be potassium lignosulfonate and/or present at 0.04- 0.6 wt.%. Acidity regulator may be 0.05-0.15 wt.% of the composition. The composition may have a pH of from 3 to 6. Also claimed are methods of controlling and preventing disease in plants, e.g. fungal, viral or bacterial disease, such as potato blight.

Description

Intellectual Property Office Application No G132200542.5 RTM Date:16 May 2022 The following terms are registered trade marks and should be read as such wherever they occur in this document: Silwet Bioloop BorreGRO Intellectual Property Office is an operating name of the Patent Office www.gov.uk/ipo
PESTICIDAL COMPOSITION
This invention relates generally to a pesticidal composition. More specifically, although not exclusively, this invention relates to a pesticidal composition comprising lactoferrin for controlling and/or preventing disease in a plant.
The agricultural industry traditionally uses pesticidal products, such as fungicides and other agrichemicals, to prevent disease in plants. This chemically focused method, however, can often cause significant environmental damage (Aktar, 2009). In particular, bioaccumulation of agrichemicals can occur during plant treatment and can have damaging impacts on the immediate plant environment as well as the wider environment if the agrichemicals enter water systems (Carrington, 2017). These methods can also have negative health impacts on both the farmers during treatment and the end consumers who may ingest food with residual agrichemicals (Pesticide Action Network UK, 2017). In particular, long term exposure to chemical pesticides has been linked to Parkinson's disease (Gilbert, 2018), asthma (Amaral, 2014) and leukaemia (Focault et al., 2021).
Consequently, many agrichemicals that prevent plant disease are scheduled to be banned by regulatory bodies, such as the European Union (EU) (Reuters, 2021). Up until now, an issue facing the agricultural industry is that no natural and organic agrichemical composition has been shown to have the same preventative effects against plant diseases without suffering from low plant/crop yield. This has made it very challenging for the industry to move away from the use of agrichemicals without significantly impacting yields and global food security. Presently the agricultural industry loses between 26 -40% of the world's potential crop production to plant diseases (Taylor, 2017). Without crop protection, it is believed that this number could rise to 80% (OECD-FAO, 2012).
Attempts made to reduce the reliance on agrichemicals in the industry have shown some environmental improvements but present a risk to global food security due to increased disease incidence in plants/crops. This has the effect of reducing production and yields per hectare. The use of agrichemicals partially solves this problem by reducing disease incidence in plant/crops but threatens the welfare of the environment through bioaccumulation of the agrichemicals (which may in turn then also cause global food security challenges).
It would be advantageous to provide a pesticide composition that provides the same, or better, efficacy in the prevention of plant disease as the current commercially available agrichemical pesticides. It is clear that an effective pesticidal composition that does not bioaccumulate in the environment will allow regulatory bodies to outlaw the use of agrichemicals without impacting global food security. This will also have significant health benefits to the environment, farmers and end consumers.
It is therefore a first non-exclusive object of the invention to provide a pesticidal composition which avoids the use of harsh agrichemicals and exhibits comparable/improved efficacy in the prevention of plant disease when compared with current commercial pesticidal compositions.
Accordingly, a first aspect of the invention provides a pesticidal composition for controlling and/or preventing disease in a plant, the pesticidal composition comprising lactoferrin, an aqueous base, and preferably one or more of an antifoaming agent, a preservative, a nonionic surfactant, a soil conditioner and an acidity regulator.
Through rigorous investigations, the inventors have found that the use of lactoferrin, for example in combination with a number of food-grade additives, in a pesticidal composition offers a number of surprising advantages when compared to commercially used pesticides such as improved efficacy in the control and/or prevention of plant diseases as well as mitigating the negatory effects associated with the use of harsh agrichemicals.
Lactoferrin is a protein which is a member of the transferrin protein family, known for a high affinity for Fe species. Typically, lactoferrin has a molecular weight of 60-100 kDa. Suitably, lactoferrin has a molecular weight of 70 -90 kDa. More suitably, lactoferrin has a molecular weight of 80 kDa.
Advantageously, the pesticidal composition of the invention does not rely on harsh agrichemicals, meaning that the pesticidal composition of the invention is a step away from the commercial norm and can facilitate the outlawing of a number of agrichemicals which are putting the welfare of the environment, farmers and end consumers at risk. Lactoferrin is found in various secretory fluids, such as milk, saliva and tears in mammals. The lactoferrin may be recombinant lactoferrin or mammalian lactoferrin, for example human lactoferrin or bovine lactoferrin or a combination thereof. The lactoferrin may be selected from apolactoferrin (iron-free), rronoferric iactoferrin (containing one ferric ion), or hololactoferrin (containing two iron ions). Preferably the lactoferrin comprises or is iron-free lactoferrin.
In the pesticidal composition of the invention, the concentration of lactoferrin can be finely tuned depending on the plant and the disease to be controlled/prevented. Suitably, the lactoferrin has a concentration of 0.001 -10 wt%. More suitably, the lactoferrin has a concentration of 0.0025 -8 wt%. Yet more suitably, the lactoferrin has a concentration of 0.005 -7.5 wt °/0. In an embodiment, the lactoferrin has a concentration of 0.05 -5 wt%. The pesticidal composition may comprise less than 5 wt%, for example less than 4, 3, 2, or 1 wt%. In an embodiment the concentration of lactoferrin is from 0.01 -3 wt% lactoferrin. Suitably, the pesticidal composition comprises 0.01 -2.5 wt% lactoferrin. More suitably, the pesticidal composition comprises 0.01 -2.25 wt% lactoferrin. In an embodiment, the pesticidal composition comprises up to 2 wt% lactoferrin.
The aqueous base may be a solvent, in which case the aqueous base may dissolve and/or dilute the ingredients (e.g., lactoferrin) in the pesticidal composition of the invention. The aqueous base may be a carrier, in which case the aqueous base may aid the delivery of the lactoferrin to a desired target. The aqueous base may be an adjuvant, in which case the aqueous base may aid the pesticidal composition being applied to a target (e.g., greater surface coverage and/or improved retention on the target).
The aqueous base may comprise greater than 80 wt% water. Suitably, the aqueous base comprises greater than 90 wt% water. More suitably, the aqueous base comprises greater than 95 wt% water. Yet more suitably, the aqueous base comprises greater than 97% water. Even more suitably, the aqueous base comprises greater than 99% water. In an embodiment, the aqueous base consists of water (i.e., 100% water). In embodiments wherein the aqueous base does not consist of water, the aqueous base may comprise one or more additives. For example, the aqueous base may comprise a spray enhancer which can reduce the surface tension of the pesticidal composition. In particular, it is thought that the spray enhancer can reduce the contact angle of the pesticidal composition on foliar surfaces, thereby promoting increased surface coverage. The spray enhancer may have a viscosity (measured at 25 °C) of 0.018 -0.026 Pa*s (18 -26 cP). Suitably, the spray enhancer has a viscosity of 0.02 -0.024 Pa*s (20 -24 cP). More suitably, the spray enhancer has a viscosity of 0.021 -0.023 Pa*s (21 -23 cP). Yet more suitably, the spray enhancer has a viscosity of 0.022 Pa*s (22 cP). In an embodiment, the spray enhancer comprises Silwet ECO Super Spreader available form Momenfive Performance Materials Inc of Waterford, NY. It will be understood that Silwet ECO Super Spreader as referred to herein will comprise the properties and function of the spray enhancer as defined herein.
The aqueous base may make up to 98 or 99 wt% of the pesticidal composition. Suitably, the pesticidal composition comprises 90 -98 wt% aqueous base. More suitably, the pesticidal composition comprises above 90, 91, 92, 93, 94, 95, 96 wt% aqueous base. In an embodiment, the pesticidal composition comprises from 95 -99 wt % aqueous base.
In an embodiment, the pesticidal composition comprises 96 -98 wt % aqueous base and the aqueous base comprises greater than 90 wt% water. In an embodiment, the pesticidal composition comprises 97 -98 wt % aqueous base and the aqueous base comprises greater than 97 wt% water.
In an embodiment, the pesticidal composition comprises up to 3 wt%, e.g., from 1 -3 wt% lactoferrin and up to 97 wt% e.g., 96 -97 wt% of the aqueous base.
Antifoaming agents may reduce and/or prevent foam or the generation of foam in the pesticidal composition of the invention. The antifoam may also be able to improve the dispersion of the ingredients in the pesticidal composition of the invention to improve the overall stability. This is particularly advantageous for storage of the pesticidal composition of the invention. The antifoaming agent may comprise silicone. The antifoaming agent may be an emulsion. Thus, the antifoaming agent may comprise a silicone emulsion. The antifoaming agent may have a viscosity (measured using a Brookfield [VT viscometer, spindle No. 3, at 30 rpm and 25 °C) of 1.0-2.0 Pass (1000 -2000 cP). Suitably, the antifoaming agent has a viscosity of 1.0 -1.5 Pass (1000-1500 cP). More suitably, the antifoaming agent has a viscosity of 1.1 -1.3 Pass (1100-1300 cP). Yet more suitably, the antifoaming agent has a viscosity of 1.2 Pass (1200 cP). In an embodiment, the antifoaming agent comprises SAG 1572 available form Momentive Performance Materials Inc of Waterford, NY. It will be understood that SAG 1572 as referred to herein will comprise the properties and function of the antifoaming agent as defined herein.
The pesticidal composition may comprise 0.01 -0.07 wt% of the antifoaming agent. Suitably, the pesticidal composition comprises 0.02 -0.06 wt% of the antifoaming agent. More suitably, the pesticidal composition comprises 0.03 -0.05 wt% of the antifoaming agent. In an embodiment, the pesticidal composition comprises 0.04 wt% of the antifoaming agent.
In an embodiment, the pesticidal composition comprises 0.01 -0.07 wt% of the antifoaming agent and the antifoaming agent comprises silicone. In an embodiment, the pesticidal composition comprises 0.03 -0.05 wt% of the antifoaming agent and the antifoaming agent comprises a silicon emulsion.
The preservative may maintain the physical properties of the ingredients in the pesticidal composition of the invention. The preservative may also increase the ease at which the pesticidal composition of the invention is stored, facilitating commercial steps such as distribution. Suitably, the preservative is selected from the group consisting of sorbic acid, potassium sorbate, benzoic acid, sodium benzoate, potassium benzoate, calcium benzoate, ethyl p-hydroxybenzoate, sodium ethyl p-hydroxybenzoate, methyl p-hydroxybenzoate, sodium methyl p-hydroxybenzoate, sulphur dioxide, sodium sulphite, sodium hydrogen sulphite, sodium metabisulphite, potassium metabisulphite, calcium sulphite, calcium hydrogen sulphite, potassium hydrogen sulphite, nisin, natamycin, hexamethylene tetramine, dimethyl decarbonate, ethyl lauroyl arginate, potassium nitrite, sodium nitrite, sodium nitrate, potassium nitrate, propionic acid, sodium propionate, calcium propionate, potassium propionate, boric acid, sodium tetraborate and lysozyme. Suitably, the preservative is sorbic acid or potassium sorbate. In an embodiment, the preservative is potassium sorbate.
The pesticidal composition may comprise 0.01 -0.4 wt% of the preservative. Suitably, the pesticidal composition comprises 0.1 -0.3 wt% of the preservative. More suitably, the pesticidal composition comprises 0.15 -0.25 wt% of the preservative. In an embodiment, the pesticidal composition comprises 0.2 wt% of the preservative.
In an embodiment, the pesticidal composition comprises 0.1 -0.3 wt% of the preservative and the preservative is sorbic acid or potassium sorbate. In an embodiment, the pesticidal composition comprises 0.15 -0.25 wt% of the preservative and the preservative is potassium sorbate.
In an embodiment, the pesticidal composition comprises 1 -3 wt% lactoferrin, 96 -98 wt% of the aqueous base and 0.01 -0.4 wt% of the preservative. In an embodiment, the pesticidal composition comprises 1.75 -2.25 wt% lactoferrin, 97 -98 wt% of the aqueous base and 0.15 -0.25 wt% of the preservative.
The non-ionic surfactant may facilitate the surface properties of the pesticidal composition of the invention (e.g., augmenting emulsification, dispersion and spreading). The non-ionic surfactant may comprise one or more soybean hydrophobic portions. Suitably, the non-ionic surfactant comprises two soybean hydrophobic portions. The non-ionic surfactant may comprise a polyethylene glycol (PEG) hydrophilic portion. Suitably, the non-ionic surfactant comprises two soybean hydrophobic portions and a PEG hydrophilic portion. In an embodiment, the non-ionic surfactant comprises BioLoop 56L available from Lankem Ltd of Cheshire UK. Preferably the non-ionic surfactant is water soluble and has a neutral or substantially neutral (pH 6-8) pH. It will be understood that BioLoop 56L as referred to herein will comprise the properties and function of the non-ionic surfactant as defined herein.
The pesticidal composition may comprise 0.01 -0.2 wt% of the non-ionic surfactant. Suitably, the pesticidal composition comprises 0.025 -0.0175 wt% of the non-ionic surfactant. More suitably, the pesticidal composition comprises 0.05 -0.15 wt% of the non-ionic surfactant. In an embodiment, the pesticidal composition comprises 0.1 wt% of the non-ionic surfactant.
The soil conditioner may enrich the soil when applied. This has the advantageous effect of increasing plant growth and crop production. The soil conditioner may comprise a wood-based biopolymer. The soil conditioner may comprise lignin. Suitably, the soil conditioner comprises lignosulphonate. More suitably, the soil conditioner comprises potassium lignosulphonate. The soil conditioner may comprise a lignin-biopolymer. Suitably, the soil conditioner comprises a lignosulphonate-biopolymer. More suitably, the soil conditioner comprises a potassium lignosulphonate-biopolymer. The soil conditioner may comprise BorreGRO K supplied by Borregaard of Sarpsborg, Norway. It will be understood that Borregro K as referred to herein will comprise the properties and function of the soil conditioner as defined herein.
The pesticidal composition may comprise 0.3 -0.7 wt% of the soil conditioner. Suitably, the pesticidal composition comprises 0.4 -0.6 wt% of the soil conditioner. More suitably, the pesticidal composition comprises 0.45 -0.55 wt% of the soil conditioner. In an embodiment, the pesticidal composition comprises 0.5 wt% of the soil conditioner.
In an embodiment, the pesticidal composition comprises 0.3 -0.7 wt% of the soil conditioner and the soil conditioner comprises lignin. In an embodiment, the pesticidal composition comprises 0.45 -0.55 wt% of the soil conditioner and the soil conditioner comprises potassium lignosulphonate The acidity regulator advantageously controls the pH of the pesticidal composition of the invention. The acidity regulator may be selected from the group consisting of acetic acid, adipic acid, ammonia solution, ammonium acetate, ammonium hydroxide, ammonium bicarbonate, citric acid, disodium fumarate, disodium malate, ferric ammonium citrate, fumaric acid, glucono delta-lactone, lactic acid, magnesium citrate, magnesium hydroxide, malic acid, monosodium fumarate, phosphoric acid, potassium acetate, potassium adipate, potassium bitartrate, potassium citrate, potassium sodium tartrate, potassium tartrate, sodium adipate, sodium hydroxide, sodium lactate, tartaric acid and trisodium citrate, or a hydrate thereof (e.g., citric acid monohydrate). Suitably, the acidity regulator is citric acid or citric acid monohydrate. In an embodiment, the acidity regulator is citric acid monohydrate.
The pesticidal composition may comprise 0.01 -0.2 wt% of the acidity regulator. Suitably, the pesticidal composition comprises 0.025 -0.0175 wt% of the acidity regulator. More suitably, the pesticidal composition comprises 0.05 -0.15 wt% of the acidity regulator. In an embodiment, the pesticidal composition comprises 0.1 wt% of the acidity regulator.
In an embodiment, the pesticidal composition comprises 0.01 -0.2 wt% of the acidity regulator and the acidity regulator is citric acid or citric acid monohydrate. In an embodiment, the pesticidal composition comprises 0.05 -0.15 wt% of the acidity regulator and the acidity regulator is citric acid monohydrate.
The pesticidal composition may have a pH of 3 -8. Suitably, the pesticidal composition has a pH of 4 -6. In an embodiment, the pesticidal composition has a pH of 4.6 -5.2.
In an embodiment, the pesticidal composition comprises: * 1 -3 wt% lactoferrin * 96 -98 wt% of the aqueous base * 0.01 -0.07 wt% of the antifoaming agent * 0.01 -0.4 wt% of the preservative * 0.01 -0.2 wt% of the non-ionic surfactant * 0.3 -0.7 wt% of the soil conditioner * 0.01 -0.2 wt% of the acidity regulator In an embodiment, the pesticidal composition comprises: * 1.5-2.5 wt% lactoferrin * 97 -98 wt% of the aqueous base * 0.02 -0.06 wt% of the antifoaming agent * 0.1 -0.3 wt% of the preservative * 0.025 -0.0175 wt% of the non-ionic surfactant * 0.4 -0.6 wt% of the soil conditioner * 0.025 -0.0175 wt% of the acidity regulator In an embodiment, the pesticidal composition comprises: * 1.75 -2.25 wt% lactoferrin * 97.4 -97.8 wt% of the aqueous base * 0.03-0.05 wt% of the antifoaming agent * 0.15-0.25 wt% of the preservative * 0.05 -0.15 wt% of the non-ionic surfactant * 0.45 -0.55 wt% of the soil conditioner * 0.05 -0.15 wt% of the acidity regulator In an embodiment, the pesticidal composition comprises: * 2 wt% lactoferrin * 97.6 wt % of the aqueous base * 0.04 wt% of the antifoaming agent.
* 0.2 wt% of the preservative.
* 0.1 wt% of the non-ionic surfactant.
* 0.5 wt% of the soil conditioner.
* 0.1 wt% of the acidity regulator.
Unless otherwise specified, where the quantity of a particular component of a given product is specified as a weight percentage (wt%), said weight percentage refers to the percentage of said component by weight relative to the total weight of the product as a whole (i.e., the pesticidal composition). It will be understood by those skilled in the art that the sum of weight percentages of all components of a product will total 100 wt%. However, where not all components are listed (e.g., where a product is said to "comprise" one or more particular components), the weight percentage balance may optionally be made up to 100 wt% by unspecified ingredients.
A further aspect of the invention provides a method of controlling and/or preventing diseases in plants, the method comprising applying an agronomically effective and substantially nonphytotoxic quantity of a pesticidal composition according to the first aspect of the invention to seeds of plants, to plants themselves, to an area adjacent to a plant, to soil in contact with a plant, to soil adjacent to a plant, to an area where it is intended that plants will grow or to agricultural equipment.
A yet further aspect of the invention provides a method of treating diseases in plants, the method comprising applying an agronomically effective and substantially non-phytotoxic quantity of a pesticidal composition according to the first aspect of the invention to seeds of plants, to plants themselves, to an area adjacent to a plant, to soil in contact with a plant, to soil adjacent to a plant, to an area where it is intended that plants will grow or to agricultural equipment.
Through rigorous investigations, the inventors have found that the pesticidal composition of the invention is particularly effective in the control, prevention and/or treatment of plant disease in an area to which the pesticidal composition of the invention has been applied. It is known in plant diseases that in order to infect a host, a virus will spike a cell and infect this cell with a viral envelope. The viral envelope then allows for the proliferation of the virus within the host, following which the virus is able to infect and proliferate more within the host. The majority of the currently used agrichemicals enable the prevention of plant diseases through a process of killing the virus by utilising disinfectant biocides. The approach of the present invention is different. The inventors have theorised that the natural compounds within the pesticidal composition of the invention control, prevent and/or treat plant diseases by inhibiting both the cellular attachment of plant viruses onto the plant and inhibiting viral replication in the cells by inducing antiviral cytokines interferon (IFN)-0/13. In vitro studies intimate that lactoferrin inhibits cellular attachment and viral replication within cells by inducing antiviral cytokines interferon. Furthermore, as an iron-binding protein with a very high affinity for Fe species, it is also theorised that many pathogenic bacteria, which are reliant on a supply of free iron to multiply, are inhibited and/or killed by the presence of lactoferrin in the pesticidal composition of the invention.
The disease may be a pathogenic fungal disease, a pathogenic viral disease or a pathogenic bacterial disease.
The disease may be selected from the group consisting of anthracnose, apple scab, black knot, blossom end rot, brown rot, rust (e.g., cedar apple rust), club root, corn smut, crown gall, damping off, fusarium wilt, grey mold, leaf spot, black spot, mosaic virus, peach leaf curl, potato scab, powdery mildew, downy mildew, blight (e.g., early blight, late blight/potato blight, foliar blight or fire blight), potato spindle tuber viroid and canker. Suitably, the disease is selected from the group consisting of grey mold, powdery mildew, downy mildew, blight (e.g., early blight, late blight/potato blight, foliar blight or fire blight) and potato spindle tuber.
The step of applying an agronomically effective and substantially non-phytotoxic quantity of a pesticidal composition according to the invention may be by seed treatment, treatment using a hydroponic system and/or spray coating (e.g., spray application, aerial spraying and crop dusting). Suitably, the step of applying an agronomically effective and substantially non-phytotoxic quantity of a pesticidal composition according to the invention is by spray coating (e.g., spray application, aerial spraying and crop dusting).
Whilst not wishing nor intending to be bound by any particular theory, the inventors have also theorised that the pesticidal composition of the invention, due to the method by which the lactoferrin inhibits cellular attachment and viral replication within cells by inducing antiviral cytokines interferon, does not require application to the desired area as frequently as current commercial agrichemical pesticidal compositions. Depending on humidity levels, a typical agrichemical pesticide needs to be sprayed as a prophylactic to plant disease every 5-8 days. The period of time between the step of applying an agronomically effective and substantially non-phytotoxic quantity of a pesticidal composition according to the invention to a desired area and repeating this step may be greater than 8 days. Suitably, the period of time between the step of applying an agronomically effective and substantially non-phytotoxic quantity of a pesticidal composition according to the invention to a desired area and repeating this step may be greater than 10 days. More suitably, the period of time between the step of applying an agronomically effective and substantially non-phytotoxic quantity of a pesticidal composition according to the invention to a desired area and repeating this step may be greater than 12 days. Providing a greater length of time between repeating steps reduces the need for farmers to drive over their fields in order to spray chemical pesticides, thereby reducing fossil fuel consumption from tractors and damage caused to plants by tractor tracks.
The agricultural equipment may be selected the group consisting of tractors, cultivators, culfipackers, ploughs, harrow, land imprinters, stone / rock / debris removal implements, subsoilers, rotators, rollers, strip till toolbars, trowels, seed-counting machines, seed drills, planters, liquid manure/slurry spreaders, Liquid manure fertilizer spreaders, dry Manure spreaders, sprayers, buckrakes, grain carts, conveyor belts, cotton pickers, farm trucks, grain dryers, harvesters, haulm toppers, mowers, rakes, reaper-binders, rice hullers, swathers and wagons.
A yet further aspect of the invention provides use of the pesticidal composition according to the invention for controlling and/or preventing disease in a plant.
A yet further aspect of the invention provides use of the pesticidal composition according to the invention for treating disease in a plant.
The disease may be a pathogenic fungal disease, a pathogenic viral disease or a pathogenic bacterial disease.
The disease may be selected from the group consisting of anthracnose, apple scab, black knot, blossom end rot, brown rot, rust (e.g., cedar apple rust), club root, corn smut, crown gall, damping off, fusarium wilt, grey mold, leaf spot, black spot, mosaic virus, peach leaf curl, potato scab, powdery mildew, downy mildew, blight (e.g., early blight, late blight/potato blight, foliar blight or fire blight), potato spindle tuber viroid and canker. Suitably, the disease is selected from the group consisting of grey mold, powdery mildew, downy mildew, blight (e.g., early blight, late blight/potato blight, foliar blight or fire blight) and potato spindle tuber.
Within the scope of this application, it is expressly intended that the various aspects, embodiments, examples and alternatives set out in the preceding paragraphs, in the claims and/or in the following description, and in particular the individual features thereof, may be taken independently or in any combination. That is, all embodiments and/or features of any embodiment can be combined in any way and/or combination, unless such features are incompatible. For the avoidance of doubt, the terms "may", "and/or", "e.g.,", "for example" and any similar term as used herein should be interpreted as non-limiting such that any feature so-described need not be present. Indeed, any combination of optional features is expressly envisaged without departing from the scope of the invention, whether or not these are expressly claimed. The applicant reserves the right to change any originally filed claim or file any new claim accordingly, including the right to amend any originally filed claim to depend from and/or incorporate any feature of any other claim although not originally claimed in that manner.
Embodiments of the invention will now be described by way of example only and with reference to the following examples:
Example 1
A composition of the pesticidal composition of the invention was formulated as shown in Table 1.
Table
Compound Action Per Litre Water Base 970.6g Lactoferrin Active 20.0g SAG 1572 Antifoaming agent 0.4g Potassium Sorbate Preservative 2.0g BioLoop 56L surfactant Non-ionic surfactant 1.0g Borregro K Soil Conditioner 5.0g Citric Acid Monohydrate Acidity regulator 1.00g Total 1000g Advantageously, the inventors have devised a natural and organic pesticidal composition to be used within the arable and horticultural farming industry. The formulation involves the utilisation of lactoferrin, with the optional addition of potassium sorbate, citric acid, a soil conditioner, a non-ionic surfactant and antifoam. The lactoferrin and aforementioned additives are suitable for use in organic farming. Whilst not wishing or intending to be bound by any particular theory, the inventors have theorised that the additives advantageously increase the performance of lactoferrin by reducing the surface tension of the spray water thus promoting increased surface coverage, while enhancing retention and plant uptake of essential macro and micro-nutrients. Such a strategy allows for increasing biomass production, but also induces the natural resistance of plants and improves the nutraceufical quality of plant food. Thus, the pesticidal composition of the invention is a viable alternative to commercial pesticides without suffering from the drawbacks associated with the use of harmful agrichemicals. Not only this, the use of the additives in combination with the lactoferrin prevent degradation and denaturation of the organic pesticidal composition, a drawback often associated with the shelf life of natural and organic formulations.
Example 2
The samples listed in Table 2 were investigated for their resistance against Phytophthora infestans, which is a fungus-like microorganism associated with potato blight.
Table 2
Sample Compound Concentration (wt%) 1 Lactoferrin 0.5 2 Lactoferrin 1 3 Lactoferrin 2.5 4 Lactoferrin 5 Stevia 1 6 Stevia 2 7 Stevia 5 8 Water 9 No spray (control) No infection (control) Assay Spray/Detached Leaf Test.
Preparation of samples and controls (solvent/solubility/concentration) Samples: 1. 0.5% lactoferrin: stock solution of 2% lactoferrin diluted x4 with water.
2. 1% lactoferrin: stock solution of 2% lactoferrin diluted x2 with water.
3. 2.5% lactoferrin: stock solution of 10% lactoferrin diluted x4 with water.
4. 5% lactoferrin: stock 10% lactoferrin diluted x2 with water.
5. 1% stevia: compound dissolved in water.
6. 2% stevia: compound dissolved in water.
7. 5% stevia: compound dissolved in water.
8. Water control The samples (including water control) were filled into small individual bottles and a spray nozzle was attached.
Spraying of Tomato leaves and infection of leaves Tomato plants (cv. Moneymaker) were grown from seed in a heated greenhouse with LED lighting and pricked out into individual pots. Plants were suitable for use when -200mm in height. Three plants were used per spray sample/control.
The plants were sprayed in the greenhouse three times over 6 days, with samples 1-7 and the water control (sample 8). The plants were sprayed on the upper and under side of the leaves until fully wetted. Three further plants were not sprayed as the no spray control (sample 9). The plants were kept fully turgid throughout the test period by careful watering at the base. The plants were also monitored for signs of any phytotoxic reaction from the samples used and this was recorded prior to infection with Phytophthora infestans.
Detached Leaf Test: Collection of leaves, number of leaves per test On the day following the 3rd spraying, 2 leaflets were removed from each plant for assessment by detached leaf test (6 leaflets per sample or control). Each set of 6 leaflets were arranged on damp paper towelling (15 mL water added to 2 sheets) in a plastic box with a loose-fitting lid.
Preparation of inoculum: spore concentration, strain of Phytophthora infestans One well-infected tomato leaflet (cv. Moneymaker) infected with G36 A2 (Phytophthora infestans of the A2 mating type) was used. Sporangia were spray-harvested in spring water, washed and made up to -10mL with spring water (i.6., 50% concentration of sporangia used for a regular detached leaf test).
Inoculation of leaves (volume, number of inoculations/leaf, placement) The prepared sporangial suspension was mixed well immediately prior to use. Four 20pL droplets of sporangial suspension were applied to each of the 6 leaflets in a box. The droplets were equally spaced apart (i.e., 24 drops/test/box).
Incubation Lids were fitted loosely and each box incubated on a north facing windowsill.
Blotting of inoculum Drops were blotted after 24 hours Scoring of results at 7 days post inoculation: number of lesions with sporulation/evidence of necrosis/photos Leaves were scored at 7 days and the number of visible lesions/evidence of necrosis was noted. Leaves were checked with a low power microscope for sporangia. Sporulation was scored + to +++++.
Phytotoxicity Results-assessed prior to infection No phytotoxicity was observed prior to infecting with Phytophthora infestans and all plants appeared to be growing normally. The leaves of the plants sprayed with lactoferrin looked shiny with a milky deposit, especially evident in the 1%, 2.5% and 5% test plants (samples 2, 3 and 4, respectively). The application of lactoferrin did not affect growth The results from the detached leaf test (scored 1st December at 7 days post infection) are shown in Table 3.
Table 3
Sample % Concentration 7 days a.i. (of 24 droplets) Sporulation & Lesion size 1 Lactoferrin 0.5% 0/24 2 Lactoferrin 1% 0/24 3 Lactoferrin 2.5% 0/24 4 Lactoferrin 5% 0/24 Stevia 1% 24/24 6 Stevia 2% 24/24 7 Stevia 5% 24/24 8 Water 24/24 9 No Spray 24/24 From Table 3, it is evident that lactoferrin prevented infection at all concentrations tested, indicating the effects of the pesticidal compositions of the invention. The leaflets to which lactoferrin was applied had a shiny appearance due to the dried-on protein.
Stevia, which is a common food additive with pesticidal properties, did not control and/or prevent the infection, even at concentrations as high as 5% (sample 7). In the stevia samples, there was no visible evidence of an inhibition of lesion growth or of any sporulation. Rather, the leaflets to which stevia was applied were indistinguishable from the leaflets of the controls (samples 8 and 9).
Example 3
Field trials investigating the effect of the pesticidal composition of the invention in the rapid canopy growth phase of late blight were conducted at Scotland's Rural University College (SRUC). Each trial plot measured 8 x 4 m and each trial was replicated 4 times for statistical analysis. The trial plots were assessed for resistance to foliar blight using the following treatments: * 9H -no treatment of the trial plot during rapid canopy phase growth.
* 6B M -treatment with Percos x 1 (@ 7 days) and Revus x/-cymoxanil x 3 or 4 (@ 7 days).8B K -treatment with a commercial standard pesticide (Mancozeb -PubChem CID 13307026).
* 9B H -treatment with the pesticidal composition of Example 1.
The variety of potato investigated was King Edwards (rated 3 for foliar blight resistance and 4 for tuber resistance). The pesticidal composition was applied 3-4 times during the during the rapid canopy growth phase of the crop. The results from the field trial are shown in Table 4.
Table 4
Plot 9H 6B M 8B K 96H Treatment 16 16 16 16 Block 1 2 3 4 fb%29Jul fb%05Aug fb%12Aug fbcYcl7Aug 0.7 0.8 0.8 1 0.83 fb%24Aug 0.8 1.5 2.5 2 1.70 fb%31Aug 20 40 35 45 35.00 fb%07Sep 75 80 80 85 80.00 From Table 4, it is evident that the resistance to foliar blight is greatest in the potato sample treated with the pesticidal composition of Example 1 after six weeks. The potato sample treated with the pesticidal composition of Example 1 showed a 28.6% increase in foliar blight resistance after five weeks when compared with the potato treated with the commercial standard pesticide and a 125% increase in foliar blight resistance after five weeks when compared with the untreated potato. After six weeks, the potato sample treated with the pesticidal composition of Example I showed a 6.25% increase in foliar blight resistance when compared with the potato treated with the commercial standard pesticide and a 13.3% increase in foliar blight resistance when compared with the untreated potato.
Example 4
pH is an important factor affecting the denaturation of lactoferrin. Through rigorous investigations it was found that the rate of lactoferrin denaturation was increased at a pH above 5.2, wherein it is theorised that the rate of protein unfolding and aggregation stages of denaturation are highest. This has been confirmed in similar studies (Saito et al.) wherein it has been reported that lactoferrin and its hydrolysates were denatured to an insoluble state by heat treatment under neutral or alkaline conditions above pH 6. In contrast, lactoferrin and its hydrolysates remain soluble after heat treatment under acidic conditions at pH 2 to 5. Interestingly, lactoferrin is particularly stable at pH 4 and high temperature. Indeed, lactoferrin resisted heating at 90°C for 5 min at pH 4 without any loss of iron-binding capacity, antigenic activity, or antibacterial activity.
At acidic pH (2 to 5), lactoferrin hydrolysates in the heated samples at 80°C to 120°C remained soluble and the solutions were clear. By contrast, at neutral and alkaline pH (6 to 10), turbidity and gel formation occurred, which was markedly increased with temperature rise. At pH 11, the lactoferrin hydrolysates in the heated samples remained soluble, but the colour of the samples became dark.
The investigations into the pH and solubility highlighted the important role of the acidity regulator in the pesticidal compositions of the invention. In particular, it is noted that citric acid has several benefits within the composition as a buffering agent as well as a preservative and a sequestrant.
Through rigorous investigations, the inventors have found that plant infection is completely suppressed by the pesticidal composition of the invention comprising lactoferrin at a concentration of 0.5% lactoferrin at pH 4.6 -5.2.
Advantageous aspects of the pesticidal composition of the invention The natural and organic nature of the pesticidal composition of the invention has highlighted that this is a viable alternative to the current commercial methods which rely on harsh agrichemicals. In particular, the pesticidal composition has been shown to display the following advantageous effects: * More efficacious when compared to industry standard * Facilitate regulatory changes * Avoids bioaccumulafion within the environment * Minimises damage to the environment, farmers and end consumers * Reduce costs to farmers through a reduction in lost produce * Increase germination rates within seeds * Increase yields of produce per hectare * Effective on a broad spectrum of plant disease (Powdery Mildew, Downy Mildew, Botrytis and the strongest strain of Blight).
It will also be appreciated by those skilled in the art that any number of combinations of the aforementioned features and/or those shown in the appended drawings provide clear advantages over the prior art and are therefore within the scope of the invention described herein.
REFERENCES
Reuters. (2021). EU court upholds ban on insecticides linked to harming bees. Available at: bttP§,:11\Yivvvieui-er,c3DiljiwatilfumPeitMcaP:(1PurturabolctkaQtar, bLxlier-Peatridfa'c'srdifikffh harm: i-bees-20211,)5- 06/#:-.:textrzEW";:20auditors9'h2Olast%20year°120said use%20by%2020%25%2Obv%202030 Aktar, Wasim & Sengupta, Dwaipayan & Chowdhury, Ashim. (2009). Impact of pesticides use in agriculture: their beneifts and hazards. Available at: ht.tps://www nebi.nlm n i h.0 ovionicia rticl erVPMC2984 095/ Amaral, Andrew F. S. (2014). Pesticides and Asthma: Challenges for Epidemiology. Available at: byl..::I/v.,,,vcDcbi. La. nithgoviipmelaridesiPMC3901 0731 Carrington, Damian. (2017). English rivers polluted by powerful insecticides, first tests reveal.
Guardian [online]. Available at: htlpSIAVAY,i.thfaigarclipri,pprnienviyarimept/20,174.1ecti3"enc iish-rivers:Do;;u. 1-1 jrigractcid(isilfiug:$st,t-reis:t)a: Gilbert, Rebecca. (2018). The Relationship Between Pesticides and Parkinson's. ADPA [online]. Available at: h ariisluwww. aim-Jana rkin son.c.:rnla rti del:iie-rela.fi shin-betwee pesticides-and: nark'ns -?0,,e * e 11:11,61 r.'fr' oF%.2DaHk2OpoHutIon.
Focault, Amelie & Vallet, Nicolas & Ravalet, Noemie & Picou, Frederic & Bene, Marie C. & Gyan, Emmanuel & Herault, Olivier. (2021). Occupational pesticide exposure increases risk of acute myeloid leukaemia: a meta-analysis of case-control studies including 3,955 cases and 9,948 controls. Available at: .https://www.,ngtur2, comiaitidcLVs4159:3-021L; 604:x Pesticide Action Network UK. (2017). Pesticides in our Food. Available at: hitusliwww.anuk.oratour-foccil Taylor, Graeme. (2017). Pesticides: with or without? Global Food Security [online]. Available at: https:!/www.Foodscvrty. foodsecur:ty. b Thesticides-with o. will out/ OECD-FAO Agricultural Outlook (2012), OECD, Food and Agriculture Organization of the United Nations, OECD Publishing, 11 Jul 2012 -286 pages

Claims (24)

  1. CLAIMS1. A pesticidal composition for controlling and/or preventing disease in a plant, the pesticidal composition comprising lactoferrin, an aqueous base, and optionally one or more of an antifoaming agent, a preservative, a non-ionic surfactant, a soil conditioner and an acidity regulator.
  2. 2. The pesticidal composition of claim 1, wherein the pesticidal composition comprises up to 8 wt% lactoferrin.
  3. 3. The pesticidal composition of any one of claims 1 or 2, wherein the lactoferrin has a concentration of 0.005 -7.5 wt%.
  4. 4. The pesticidal composition of any one of the preceding claims, wherein the aqueous base comprises greater than 95 wt% water.
  5. 5. The pesticidal composition of any one of the preceding claims, wherein the pesticidal composition comprises up to 98 or 99wt% aqueous base.
  6. 6. The pesticidal composition of any one of the preceding claims, wherein the antifoaming agent comprises silicone, preferably wherein the antifoaming agent comprises a silicone emulsion.
  7. 7. The pesticidal composition of any one of the preceding claims, wherein the pesticidal composition comprises 0.02 -0.06 wt% of the antifoaming agent.
  8. 8. The pesticidal composition of any one of the preceding claims, wherein the preservative is selected from the group consisting of sorbic acid, potassium sorbate, benzoic acid, sodium benzoate, potassium benzoate, calcium benzoate, ethyl p-hydroxybenzoate, sodium ethyl p-hydroxybenzoate, methyl p-hydroxybenzoate, sodium methyl phydroxybenzoate, sulphur dioxide, sodium sulphite, sodium hydrogen sulphite, sodium metabisulphite, potassium metabisulphite, calcium sulphite, calcium hydrogen sulphite, potassium hydrogen sulphite, nisin, natamycin, hexamethylene tetramine, dimethyl decarbonate, ethyl lauroyl arginate, potassium nitrite, sodium nitrite, sodium nitrate, potassium nitrate, propionic acid, sodium propionate, calcium propionate, potassium propionate, boric acid, sodium tetraborate and lysozyme.
  9. 9. The pesticidal composition of any one of the preceding claims, wherein the pesticidal composition comprises 0.1 -0.3 wt% of the preservative
  10. 10. The pesticidal composition of any one of the preceding claims, wherein the non-ionic surfactant comprises one or more soybean hydrophobic portions.
  11. 11. The pesticidal composition of any one of the preceding claims, wherein the pesticidal composition comprises 0.05 -0.15 wt% of the non-ionic surfactant.
  12. 12. The pesticidal composition of any one of the preceding claims, wherein the soil conditioner comprises lignin, preferably wherein the soil conditioner comprises lignosulphonate.
  13. 13. The pesticidal composition of any one of the preceding claims, wherein the soil conditioner comprises potassium lignosulphonate.
  14. 14. The pesticidal composition of any one of the preceding claims, wherein the pesticidal composition comprises 0.4 -0.6 wt% of the soil conditioner.
  15. 15. The pesticidal composition of any one of the preceding claims, wherein the acidity regulator is selected from the group consisting of acetic acid, adipic acid, ammonia solution, ammonium acetate, ammonium hydroxide, ammonium bicarbonate, citric acid, disodium fumarate, disodium malate, ferric ammonium citrate, fumaric acid, glucono delta-lactone, lactic acid, magnesium citrate, magnesium hydroxide, malic acid, monosodium fumarate, phosphoric acid, potassium acetate, potassium adipate, potassium bitartrate, potassium citrate, potassium sodium tartrate, potassium tartrate, sodium adipate, sodium hydroxide, sodium lactate, tartaric acid and trisodium citrate, or a hydrate thereof (e.g., citric acid monohydrate).
  16. 16. The pesticidal composition of any one of the preceding claims, wherein the pesticidal composition comprises 0.05 -0.15 wt% of the acidity regulator.
  17. 17. The pesticidal composition of any one of the preceding claims, wherein the pesticidal composition has a pH of 3 -6, preferably wherein, the pesticidal composition has a pH of 4 -5.5.
  18. 18. A method of controlling and/or preventing diseases in plants, the method comprising applying an agronomically effective and substantially non-phytotoxic quantity of a pesticidal composition of any one of claims 1-17 to seeds of plants, to plants themselves, to an area adjacent to a plant, to soil in contact with a plant, to soil adjacent to a plant, to an area where it is intended that plants will grow or to agricultural equipment.
  19. 19 A method of treating or preventing diseases in plants, the method comprising applying an agronomically effective and substantially non-phytotoxic quantity of a pesticidal composition of any one of claims 1-17 to seeds of plants, to plants themselves, to an area adjacent to a plant, to soil in contact with a plant, to soil adjacent to a plant, to an area where it is intended that plants will grow or to agricultural equipment.
  20. 20. The method of any one of claims 18 or 19, wherein the disease is a pathogenic fungal disease, a pathogenic viral disease or a pathogenic bacterial disease.
  21. 21. The method of any one of claims 18, 19 or 20, wherein the disease is selected from the group consisting of anthracnose, apple scab, black knot, blossom end rot, brown rot, rust (e.g., cedar apple rust), club root, corn smut, crown gall, damping off, fusarium wilt, grey mold, leaf spot, black spot, mosaic virus, peach leaf curl, potato scab, powdery mildew, downy mildew, blight (e.g., early blight, late blight/potato blight, foliar blight or fire blight), potato spindle tuber viroid and canker.
  22. 22. The method of any one of claims 18, 19, 20 or 21, wherein the step of applying an agronomically effective and substantially non-phytotoxic quantity of a pesticidal composition of any one of claims 1-17 is by seed treatment and/or spray coating (e.g., spray application, aerial spraying and crop dusting).
  23. 23. Use of a pesticidal composition of any one of claims 1-17 for controlling and/or preventing disease in a plant.
  24. 24. Use of lactoferrin in the prevention or treatment of diseases in plants, comprising applying a lactoferrin composition comprising an aqueous base to one or more plants.Use according to Claim 23 or 24 comprising applying the composition to plants at most, once every 8 days, for example at most once every 9 days
GB2200542.5A 2022-01-18 2022-01-18 Pesticidal composition Pending GB2614742A (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
US20040235711A1 (en) * 2001-06-27 2004-11-25 Katsuo Kumagai Immunopotentiator for mammary gland of dairy cows containing lactoferrin as an active ingredient
US20060247130A1 (en) * 2003-01-27 2006-11-02 Van Der Krieken Wilhelmus M Compositions comprising lignosulfonates for crop protection and crop improvement
US20070265478A1 (en) * 2006-05-09 2007-11-15 Ulsan Chemical Co., Ltd. Dry-etching gas for semiconductor process and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040235711A1 (en) * 2001-06-27 2004-11-25 Katsuo Kumagai Immunopotentiator for mammary gland of dairy cows containing lactoferrin as an active ingredient
US20060247130A1 (en) * 2003-01-27 2006-11-02 Van Der Krieken Wilhelmus M Compositions comprising lignosulfonates for crop protection and crop improvement
US20070265478A1 (en) * 2006-05-09 2007-11-15 Ulsan Chemical Co., Ltd. Dry-etching gas for semiconductor process and preparation method thereof

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Title
International Journal of Food Microbiology, Vol. 161, No. 3, 2013, J WANG, "Inhibitory effect of lactoferrin against gray mould on tomato plants caused by Botrytis cinerea and possible mechanisms of action", pages 151-157 *
Plant Disease, Vol. 92, No. 12, 2013, M R SOSNOWSKI, "Evaluating Treatments and Spray Application for the Protection of Grapevine Pruning Wounds from Infection by Eutypa Lata", see pages 1599-1604 *
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