GB2514874A

GB2514874A - Plant protection composition and method

Info

Publication number: GB2514874A
Application number: GB1401930.1A
Authority: GB
Inventors: Ian Stanley Ripley
Original assignee: PHYTO INNOVATIVE PRODUCTS Ltd
Current assignee: PHYTO INNOVATIVE PRODUCTS Ltd
Priority date: 2013-02-05
Filing date: 2014-02-05
Publication date: 2014-12-10
Also published as: GB201401930D0; WO2014122446A1; GB201302034D0

Abstract

A plant protection composition comprises at least one fatty acid chain of between 2 and 10 carbons in length and flavonoid content. Preferably the flavonoid content comprises at least naringin and neohesperidin but in some embodiments the flavonoid content may comprise one or more compounds selected from the group of neoeriocitrin, iosnaringin, hesperidin, neodiosmin, naringenin, poncirin and rhiofolin. Preferably the at least one fatty acid is contained in, or derived from, a triglyceride oil. The composition may be used to restore and/or maintain plant health in response to a pathogenic attack or may be used in agriculture, horticulture or home gardening. Also claimed are methods for producing a metastable micro emulsion containing the plant protection composition and a method of applying the composition to plants or post harvest food stock by means of spraying, fogging or as a process wash.

Description

Plant Protection Composition and Method The present invention relates to a plant protection composition comprising at least one fatty acid chain of between 2 and 10 carbons in length and flavonoid content, suitable for use in agriculture, horticulture and home gardening. The plant protection composition is effective at restoring, maintaining and improving the health of plants.

More specifically, the plant protection composition provides, as a minimum, an anti-fungal function. Furthermore, the present invention provides methods of producing such compositions and their specific uses.

Consumer demand for residue-free food and an awareness of the occupational hazards posed by some synthetic pesticides has set the stage for more natural alternatives in our food production systems. Over the years many traditional chemical pesticides have been banned from use following the discovery of their harmful side-effects. In line with this, the organic food movement has grown substantially over recent years and the trend is predicted to continue. In view of this it has become important to find compositions that come from entirely natural sources which fit in with the organic food movement and which are effective at restoring, maintaining and improving the health of crops and foodstuffs. Whilst a number of organic or natural pesticides and health iruprovers for plants have been developed it is often a problem finding natural compositions which are sufficiently effective to be useful. In particular, although a number of anti-oxidants have been identified, there are few available anti-fungal compositions.

The term flavonoid encompasses a wide variety of differing compounds which are widely distributed in plants and can be extracted therefrom. Flavanoids have been classified according to their chemical structures and are typically divided into the following skeletal 3 ringed subgroups: anthoxanthins, flavanones, flavanonols, flavans, anthocyanidins and isoflavonoids. Functional groups that can be present on one or more of the 3 rings include hydroxyl groups, sugar groups, ketone groups.

A variety of flavonoids have been suggested as antioxidant, antibacterial agents and elicitors for the production of phytoalexins. PCT/GB2007/002756 and PCT/GB2007/002758 described particularly effective oral (e.g. toothpaste, mouthwash and dental rinses) compositions containing flavonoids which exhibited antibacterial activity.

Plant pesticides are intended to be applied to or introduced in to plants at low levels to avoid harmful risks to human and non-target animal life which contact and consume treated plants. In particular, pesticide residues left on the surface of plant food stocks can easily enter human and livestock food chains and water supplies.

Over recent years, particularly in developed countries, there have been moves to remove harmful and toxic chemical pesticides from use. This has prompted development of less harmful alternatives to chemical fungicides and antibacteriosides, particularly for application to food stock plants.

Plant protection compositions are compositions which can be used to formulate products designed to restore, maintain or improve healthy plant life. In particular they can be used in response to (for example) pathogenic attack to restore plant health, or they may be used as a prophylactic treatment to maintain the health of plants.

Furthermore, they may include active agents which promote the health of the plant, such that the treated plant shows improved health and harvested food crops over and above untreated plants, when subject to equivalent environmental conditions.

Suitably, the present plant protection compositions provide natural and effective plant treatments which have been designed to restore, maintain or improve healthy plant life. In one aspect they provide, as a minimum, an antifungal function, and are suitable for use in agriculture, horticulture and home gardening.

Although the present application is primarily concerned with plant protection compositions, it will be appreciated by the person skilled in the art, that the disclosed compositions are not restricted to use in treatment of plants, and have wider utility, for example in the treatment of infections (for example fungal infections) in humans and animals.

The beneficial properties of the present plant protection compositions resides in the presence of comprising at least one fatty acid chain of between 2 and 10 carbons in length and flavonoid content. These two active components can be supplemented with other active components to provide compositions with multi-functioning properties. This facilitates the provision of multi-functioning plant protection compositions, which minimise the need for multiple product applications to plants.

Accordingly, the first aspect of the present invention provides a plant protection composition comprising at least one fatty acid chain of between 2 and 10 carbons in length and flavonoid content.

This combination of active components surprisingly restores, maintains and improves the health of plants. In particular it can be used in response to pathogenic attack to restore plant health and to improve the health of plants by stimulating multi nutrient uptake. It is suitable for topical application to actively growing plants andlor harvested food stocks in an agricultural, horticultural or home gardening setting.

Preferably at least one fatty acid chain of between 2 and 10 carbon atoms is an aliphatic fatty acid. The fatty acid may be cyclic or acyclic. Most preferably the fatty acid is in a straight chain form, as these have been found to have particularly good antifungal activity when coupled with a flavonoid. More specifically straight chain forms have been found to be more effective at treating the fungi Aspergi/lus Niger in plants, and also Candida yeast infections in humans. Suitable fatty acid chains may be produced by known methods, commonly either from hydrocarbons via carboxylation, or via the saponification of triglyceride oils.

As stated above, the fatty acid chains are of between 2 and 10 carbons in length.

Such relatively short chains have desirable solubility properties, and do not require the presence of a solubility agent for use. As such, the utilisation of these relatively short fatty acid chains results in cheaper and simpler products to manufacture. More preferably the fatty acid is of between 6 and 10 carbon atoms in length. Such fatty acid chains will include hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid) and decanoic acid (capric acid). These short chain fatty acids provide adequate solubility in water.

Most preferably the plant protection composition comprises the fatty acid octanoic acid (C3). Octanoic acid provides surprisingly high levels of antifungal activity and excellent solubility properties when combined with co-solvents. Octanoic acid is commercially available from Sigma-Aldrich Company Ltd, Dorset, UK.

In one particular preferred embodiment, the present invention comprises at least one fatty acid, as described above, either contained in, or derived from, a triglyceride oil.

The triglyceride oil may be naturally occurring or synthetically manufactured.

Derivation of the at least one fatty acid from the triglyceride oil is possible via saponification, such a reaction mechanism and suitable reagents are well known in the art and not considered further herein. Obviously, such a method of saponification may well result in a mixture of fatty acids being derived from any one naturally occurring or synthetic triglyceride oil. Separation of the derived fatty acids into different length fractions is also possible by methods known in the ad. For use in the present invention separation is not deemed necessary, although for some specific plant protection compositions it may be desirable to employ a certain degree of separation to increase the level of particularly preferred fatty acid chains.

Where the triglyceride oil is naturally occurring, it is suitably vegetable, fruit or nut derived. In this case fatty acids will be naturally present within said triglyceride oils.

Naturally occurring triglyceride oils particularly useful in the present invention include neem oil, palm oil, soybean oil, rapeseed oil, sunflower seed oil, peanut oil, palm kernel oil, coconut oil and olive oil amongst others which will be apparent to the person skilled in the art.

Particularly preferred naturally occurring triglyceride oils for use in the present invention are neem oil, palm kern oil and palm oil; these oils contain relatively high levels of fatty acids of the preferred shod chain lengths discussed above, including the particularly preferred octanoic acid fatty acid. As such, these triglyceride oils require no further processing to render them suitable for incorporation in to the compositions of the present invention. Palm kern oil is particularly preferred due to its relatively high levels of naturally occurring octanoic acid fatty acids. The preferred triglyceride oils, derived from vegetable sources, originate from S E Asia or other tropical/subtropical areas and are supplied by The Kerfoot Group, North Yorkshire, UK.

The inclusion of naturally occurring triglyceride oils containing the at least one fatty acid chain has manufacturing benefits, in particular the triglyceride oil can be handled as a bulk product allowing for ease of formulation even when only small percentage weights of the active fatty acid is required in the final plant protection product.

Furthermore, as the preferred neem, palm and palm kern naturally occurring triglyceride oils contain relatively high levels of the short chain fatty acids of particular interest, there is no need to further process the oils to increase the level of fatty acid.

This results in a simpler method of manufacture with cost and time savings.

Alternatively, as stated above, the triglyceride oil may be synthetic in nature.

Synthetic triglyceride oils will also inherently contain some fatty acid content rendering them suitable for utilisation in the present invention without further processing. However, the inclusion of synthetic oils is less preferred to the inclusion of naturally occurring oils in the plant protection composition; this is because the use of naturally occurring products is more acceptable to the organic food movement, and also, the naturally occurring oils will inherently contain higher levels of fatty acids of the preferred forms as described above and below.

As alluded to above, in some cases it may be desirable to provide higher levels of the suitable fatty acids in the natural or synthetic triglyceride oil in which they are inherently contained. In this regard the percentage fatty acids present in the natural or synthetic triglyceride oils can be increased by way of partial saponification of the triglyceride oil. Saponification of neem or palm oil results in high levels of the preferred octanoic fatty acid being liberated from the triglyceride constituents. No separation of the liberated fatty acid from the bulk triglyceride is necessary, although it is possible to provide a concentrate of the fatty acid if desired for the final plant protection composition, in isolation of the triglyceride oil.

The presence of extracted fatty acid from the triglyceride oil in the plant protection composition is preferred. In palm kern oil the preferred fatty acid can be there as the free fatty acid or as the triglyceride oil. More specifically the presence of free fatty acid from the triglyceride oil helps to maintain pH levels at a preferred range of 3 to 5 within the final plant protection composition.

The flavonoid content preferably comprises a mixture of flavonoids containing a glycosidic bond, and as such can be described as a flavonoid glycoside. Such flavonoid glycosides are found to be soluble and so advantageously provide a form of flavonoids which can be incorporated into final plant protection compositions without the need of solubility agents. As stated above the avoidance of solubility agents is advantageous. As such, the present invention preferably comprises a mixture of flavonoid glycosides and at least one fatty acid chain of between 2 and 10 carbons in length.

Preferred examples of flavonoid glycosides are glycosides of flavanone and glycosides of anthocyanidins. Most preferred are glycosides of flavanone which include naringin, hesperidin, neohesperidin and poncirin. Especially preferred are naringin and neohesperidin. As such the present invention more preferably comprises a mixture of naringin and neohesperidin and at least one fatty acid chain of between 2 and 10 carbon atoms in length.

The plant protection composition may further comprise one or more compounds having a structure according to formula (0: wherein Ri is hydroxyl or methoxyl and R2 is hydrogen, hydroxyl or methoxyl and X is hydrogen or a saccharide.

Suitably X is a saccharide consisting of a combination of two monosaccharides linked by a glycosidic bond, for example rhamnose and glucose. In other words the saccharide is preferably a disaccharide. In particular suitable disaccharides include combinations of pyranoses linked by a glycosidic bond.

Suitable disaccharides can have the structures:

OH R4O HO:H

(I) (II) Where one of R3 and R4 is H and the other is OH or both are H or both are OH.

Suitably R3 is H and R4 is OH so that the disaccharide is rutinose.

Particularly preferred flavonoid glycosides are where X is a disaccharide selected from either 6-0-(alpha-L-rhamnopyranosyl)-beta-D-glucopyranose (also known as rutinose) or 2-0-(alpha-L-rhamnopyranosyl)-beta-D-glucopyra-rose.

Suitable compounds of formula (I) include neoriocitrin, isonaringin, hesperidin, neo-diosmin, naringenin, poncirin or rhiofolin. One or more of these compounds may be present in addition to naringin and neohesperidin. A mixture of two or more of these compounds in addition to naringin and neohesperidin is particularly preferred. These listed flavonoids are soluble flavonoid glycosides, and exhibit good solubility properties. The flavonoids naringin and neohesperidin exhibit excellent solubility in water. The flavonoids described herein are biologically derived and may also be referred to as bioflavonoids.

Furthermore, it is believed that the presence of two or more flavonoids in the plant protection composition is advantageous. In particular, the use of two or more flavonoids has practical manufacturing advantages as separation of flavonoids is very costly and complex.

In the especially preferred case where the flavonoid content comprises a mixture of naringin and neohesperidin then preferably the flavonoid content comprises at least 25% by weight naringin, more preferably at least 40% by weight and more preferably still 50% by weight. A most preferable flavonoid mixture will contain up to 65% by weight naringin. Preferably the flavonoid content comprises at least 15% by weight neohesperidin, more preferably 20% by weight, and more preferably still 25% by weight. A most preferable flavonoid mixture will contain up to 35% by weight neohesperidin. In one particularly preferred embodiment the flavonoid content is a mixture of flavonoids comprising at least 75% of both neohesperidin and naringin.

Preferably the flavonoid content is naturally occurring and derived from plant matter.

Suitably the flavonoid content is derived from an extract of a citrus fruit plant, including grapefruit, bitter orange, tangerine and sweet orange, for example for glycosides of flavanone. Suitably the flavonoid content is derived from an extract of a berry fruit plant including purple grape, blueberry and raspberry, for example for glycosides of anthocyanidins. In particular, citrus fruit plant extracts contain mixtures of the above preferred soluble flavonoid glycosides neohesperidin and naringin.

More desirably the flavonoid content is a mixture of flavonoids derived from an extract of bitter oranges (Citrus Aurantium). Naringin and neohesperidin can be derived from bitter oranges. Suitable products have been sourced from bitter oranges originating from Spain, and can be provided by Esquim S.A. Barcelona, Spain.

Generally, the plant matter extract will contain the flavonoid of interest comprised within a "bio-mass". Typically the bio-mass also comprises pectins, tannins and other sugar derived materials. Preferably the bio-mass contains flavonoids in about 10% to 75% of the total biomass weight; more preferably about 30% to 60% by weight and most preferably the bio-mass contains flavonoids in about 40% to 50% by weight. The presence of a bio-mass greatly aids the solubility of the flavonoid component, particularly in water. Particularly preferable forms of bio-mass contain low molecular weight pectins making up about 40% by weight of the overall bio-mass material.

In particular where the flavonoid component is derived from an extract of bitter oranges there is no need for any mixture of flavonoids present to be separated, thus offering ease of manufacturing benefits and hence cost savings. Hence, bio-mass derived from bitter oranges containing a mixture of soluble flavonoids are particularly preferred for incorporation into the plant protection compositions of the present invention.

According to a further embodiment of the present invention there is provided a plant protection composition further comprising ascorbic acid and/or oleuropein or acetylated derivative thereof. Such a plant protection composition advantageously provides a combination of antifungal and anti-oxidant properties. Although, flavonoids are known to have antioxidant properties, the provision of the oleuropein or acetylated derivative thereof can improve the anti-oxidant and antibacterial properties of a composition as compared to its flavonoid only containing counterpart.

Preferably the oleuropein or acetylated derivative thereof is naturally occurring and derived from a plant extract, as such extracts will be nontoxic and acceptable for organic food production. However, it will be appreciated by the person skilled in the art that synthetic or semi-synthetic oleuropein or acetylated derivatives thereof can be produced and utilised in the present invention.

Preferably the oleuropein or acetylated derivative containing plant extract contains between 5% and 80% oleuropein or acetylated derivative thereof by weight of the overall extract. It is envisaged that the oleuropein or acetylated derivative containing plant extract will be utilised in the present invention without the need to isolate the oleuropein or acetylated derivative thereof from the total plant extract material.

More preferably the oleuropein or acetylated derivative thereof is derived from an extract from the leaf of the olive plant, for example olea europea. The extracts originate from Spain, Italy, Tunisia, South America and China. The supplier is Pharmapia, China.

According to a still further embodiment of the present invention there is provided a plant protection composition which also comprises a fruit acid. Such a plant protection composition advantageously provides the combination of antifungal and antimicrobial functions.

Preferably the fruit acid is citric acid, malic acid, ascorbic acid or similar. A synergistic effect exists between the flavonoid and the fruit acid to produce superior antibacterial properties in comparison to the presence of the fruit acid alone in an equivalent composition. In particular a ratio of 1:3 flavonoid:fruit acid gives the best synergistic effects. In particular ascorbic acid is the preferred fruit acid as it offers good antibacterial effects, has no toxicity issues for food stock consumers and possesses excellent anti-oxidant properties.

Suitably the fruit acid may be derived from the same plant as one or more of the flavonoids. As such, the presence of ascorbic acid or citric acid derived from citrus fruits is preferred. Most preferably ascorbic acid is present in the plant protection composition. The presence of ascorbic acid may provide further advantageous functions, including higher plant growth rates and improved plant micro-nutrient up-take. (The Function and Metabolism of Ascorbic Acid in Plants, Nicholas Smirnoff, Anna/s of Botany 78:66 1 -669, 1996).

Additionally, or alternatively, the plant protection composition comprises at least one fatty acid chain of between 2 and 10 carbons in length, flavonoid content, an oleuropein or acetylated derivative thereof, and a fruit acid, such that the composition provides a multi-functional plant protection composition providing anti-fungal, anti-oxidant and anti-bacterial functionality. Where the fruit acid is ascorbic acid additional functionality by way of improved plant growth rates and micro-nutrient up-take can be provided. (The role of Ascorbic Acid in Plant Nutrition, George H. Carroll, The Botanical Review).

Preferably the plant protection composition of the present invention is diluted with water. Suitably, the compositions are manufactured in a concentrated form and diluted on site with water by the end user, prior to use, to provide a final diluted composition.

Preferably the final diluted composition, when used for topical application to plants and harvested food stocks, will contain between 99.95 and 99.50% by weight water.

It is preferred that when used for washing food stocks a concentration of active composition be less than 0.5% by weight; even such low concentrations have been found to provide an effective log 5 kill rate. It is particularly preferred that the concentrated plant protection composition be diluted with recycled or caught rain water to lessen the overall environmental impact of the product.

When used to treat a diseased plant to restore its health, the required amount of plant protection composition necessary for a satisfactory reduction in disease may need to be higher in cases of particularly high disease pressure or when environmental conditions may affect the efficacy of the product, for example during particularly high humidity. Taking these considerations into account, it is preferred that the concentrated plant protection composition be diluted for use so as to be present in the range 0.05% to 0.5% by weight of the overall final diluted composition, the remainder preferably being water as described above, i.e. 50m1 -500m1 of a concentrated composition product (which may contain some water) is diluted in 100 litres of water. As a general guideline 0.15% by weight of the concentrated product is present in the finally diluted composition i.e. 150m1 of concentrate is diluted in 100 litres of water.

Additionally, the diluted compositions of the present inventions are most effective when the final diluted composition has a low pH, in the range pH 2.5 -4. Where the pH of the water used may be significantly over the value of pH 7 it is preferable to buffer the water to approximately pH 7, so that the final pH of the diluted mixture after addition of the concentrated plant protecting composition is in the range pH 2.5 -pH 4. Buffering of the water in this way can be done by the addition of any known neutralising agent. Preferably the neutralising agent is citric acid, as this can be naturally derived, and will not result in toxic residues.

Additionally, in one embodiment of the present invention, any of the plant protection compositions described above may comprise a chelating agent. The chelating agent serves to form chelating complexes with hard water metal ions, such as calcium, magnesium and iron (Ca2t, Mg2 and Fe2'3t) which may be present in the dilution water and bind to the at least one flavonoid component thus limiting its effectiveness within the composition. Therefore, where known hard water, recycled water or caught rain water is to be included in the composition as the dilution water, then the inclusion of a chelating agent is particularly preferred.

Although any known chelating agent may be used in the compositions of the present invention, including synthetic agents such as ethylenediaminetetraacetic acid (EDTA), it is preferred that the chelating agent chosen is a naturally derived product, to avoid any undesirable residues remaining on the plants or harvested food stocks.

In particular, it is preferred that the chelating agent is an aliphatic organic acid. Such organic acids can be naturally derived and hence will not attribute to toxic residues upon treated plants or harvested food stocks and will be acceptable for organic food treatment. Most preferably the aliphatic organic acid chelating agent is lactic acid.

Lactic acid has been found to provide particularly good hard water ion chelating properties in the present compositions. In addition, citric acid may be utilised as a naturally derived chelating agent. Citric add is a known good organic chelating agent for use in water.

Alternatively, the chelating aliphatic organic acid may be an aromatic organic compound. One particularly desirable such compound is salicylic acid. Salicylic acid naturally occurs in willow bark and has no toxicity issues with respect to residues remaining upon food to be consumed.

In addition, some amino acids are known to be useful organic chelating agents, and these may also be utilised in the present invention compositions, although these are less preferable agents.

Additionally or alternatively the plant protection composition also comprises a nutrient complex. The nutrient complex provides micro and macro nutrients to a treated plant to help maintain and restore general plant health, in this regard the composition can support combined antifungal and health maintaining or restoring functions. Suitable levels of micro and macro nutrients for incorporation into nutrient complexes will be evident to the person skilled in the art. However, the addition of Iron at a level of about 0.5% by weight and/or about 0.3% by weight Magnesium and/or Zinc in a chelated form is particularly preferable. Additionally, or alternatively, addition of Copper may be preferred, this is particularly the case where the crop to be treated is a potato. In some embodiments it may be preferable to utilise controlled release mechanisms to control the rate of release of micro and macro nutrients to a plant.

Such release mechanisms will be known to the person skilled in the art.

Additionally or alternatively, the plant protection compositions of the present invention can be utilised as fertilisers, preferably incorporating potassium. Ideally, such a fertiliser will incorporate potassium at a level of 18% by weight. In addition other known ingredients of fertilisers may be utilised including nitrogen at know levels, to enhance fertiliser effectiveness.

Clearly, where the composition comprises at least one fatty acid chain of between 2 and 10 carbon chain length, flavonoid content, an oleuropein or acetylated derivative thereof, a fruit acid, and/or a nutrient complex the composition provides a multi- functional plant protection composition providing anti-fungal, anti-oxidant, anti-bacterial and health improving, maintaining or restoring functionality.

However, even where the composition comprises soluble flavonoid content and at least one fatty acid chain of between 2 and 10 carbons in length it may be preferable to include a coupling agent to assist in the maintenance of the solution. The coupling agent assists in dispersing the fatty acid chains in the water component of the final product. In particular coupling agents can be selected based on the proviso that they have a hydrophilic-lipophilic balance (H [B) value of approximately 7 (that is they are emulsifiers). However, more preferably the coupling agent is fulvic acid, glycerine or ethyl alcohol; a possible alternative to fulvic acid is levulinic acid; these agents are non-toxic and safe for consumption. More particularly glycerine is preferred due to the fact that it is used in plant metabolism. Although, in some embodiments fulvic acid is preferred as it is known to have beneficial properties relating to plant root up-take of micro nutrients, and so the general health of plants may be improved by a composition comprising fulvic acid.

Additionally or alternatively, the plant protection compositions of the present invention may preferably include a surfactant, to enhance the solubility of the other composition ingredients, and to increase wetting effects. Preferably the surfactant is an alkyl glucoside.

A method of producing a metastable micro emulsion is also provided, comprising the steps of adding the components of the plant protection composition whilst continuously mixing at a high shear rate. Preferably mixing is achieved by a Silverson high shear mixer, available from Silverson Machines Ltd, Chesham Bucks, UK.

Where a coupling agent is employed, it is preferable that the coupling agent is added first and subjected to high shear mixing prior to the addition of further ingredients.

This ensures that the mixture is kept as hydrophilic in nature as possible, during the initial mixing steps. This has a stabilising effect on the micro emulsion produced and ultimately results in an oleophilic coated emulsion.

In addition, where a coupling agent is employed it is particular preferred that a surfactant is also employed to increase wetting and the solubility of further composition ingredients. Typically the coupling agent will be added to the formulation mixture first, subjected to high shear mixing, and then the surfactant will be added, prior to the addition of further ingredients.

As discussed above, preferably all agents and ingredients employed in the present compositions are non-toxic and derived from naturally occurring products and the following examples emphasise this. However, the replacement of any naturally occurring agent with a synthetic or semisynthetic equivalent offers no hurdle to the person skilled in the art. However, preferably the invention provides a treatment which is safer and more environmentally friendly than other plant protection products which are largely or wholly synthetically derived.

In addition, the inventor has found that the present preferred naturally occurring component compositions do not alter the taste of food stocks, have no irritant odour and have no residual withholding periods when used. The components of the particularly preferred embodiments of the compositions and their residues have all been proven non-toxic to humans. Also, all the components of the compositions, when naturally derived products, are acceptable for use in food. The compositions are also completely biodegradable.

Furthermore, the present compositions do not contribute to corrosion of expensive manufacturing plant equipment or equipment utilised in use. Also, the avoidance of toxic agents results in safer working conditions for the equipment operators during manufacture and use.

According to a further aspect of the present invention there is provided a use of a plant protection composition as described above as a plant treatment agent to restore and/or maintain plant health in response to pathogenic attack.

According to a further aspect of the present invention there is provided a use of a plant protection composition as described above as an antifungal agent.

Additionally or alternatively, there is provided a use of a plant protection composition as described in some particular embodiments above as an antifungal and antioxidant agent.

Additionally or alternatively, there is provided a use of a plant protection composition according to some embodiments of the above mentioned invention as an antifungal and antibacterial treatment, alone or in combination with an antioxidant agent.

Preferably the plant protection compositions as described above may be used as plant prophylactics. In this way they may help to prevent infection of treated plants by fungal agents, bacteria or other health limiting ailments.

Additionally or alternatively there is provided a use of a plant protection composition according to some embodiments of the abovementioned invention as a plant treatment agent to stimulate multi nutrient uptake of plants.

In addition, or alternatively, the compositions described above may be used for post-harvest food stock application. Such post-harvest application can limit deterioration of the food stock upon storage, which may provide a longer shelf like for treated food stock as compared to non-treated food stock.

According to a further aspect of the present invention there is also provided a method of applying a plant protection composition as described above to plants or post-harvest food stock by means of spraying, fogging or as a process wash. It is envisaged that the plant protection compositions of the present invention will be suitable to use on a large variety of fresh cut fruit and vegetable produce, including the following; stoned fruits, deciduous fruits, citrus fruits, berries, exotic or tropical fruits, tomatoes, figs, kiwi, leafy or flowery vegetables, salad crops, lettuce, root vegetables, enlarged stem vegetables, aromatic herbs, cereals, flowers, ornamental flowers, chrysanthemums, lawns and turf.

Preferably such a method employs a first step of diluting a concentrated plant protection composition according to any of the embodiments described above, with dilution water. In particular, it is preferred that the final composition be diluted to be in the range 0.05% to 0.5% by weight of the overall final composition, the remainder preferably being water as described above, i.e. 50m1 -500m1 of a concentrated composition product (which may contain some water) is diluted in 100 litres of water.

As a general guideline 0.15% by weight of the concentrated product is present in the finally diluted composition i.e. 150m1 of concentrate is diluted in 100 litres of water.

Suitably, the rate of topical application of the diluted composition and the timing of these applications must ultimately be decided depending on the environmental conditions and the amount of actual or expected disease pressure. Suitable application regimes will be known to the skilled person, or evident from simple trial and error.

Preferably the final diluted composition in use is applied to plants or harvested food stocks during the cool of the day and preferably not prior to or just subsequent to rain as this could severely reduce the efficacy of the product.

For large scale agricultural uses correct use of application machinery should be performed in order to minimise the amount of final diluted composition applied, while maximising the composition effects. Preferably, thorough mixing of the plant protection composition with the dilution water will be performed in a spray tank prior to the spraying of plants or harvested food stocks. Most preferably spraying is conducted very soon after mixing in order to avoid reduction in efficacy as a result of separation in the diluted composition. The product efficacy is expected to be higher if applied using a small droplet size (<150pm) spray delivery system, as such in use preferably an electrostatic sprayer is employed. Use of the preferred electrostatic sprayer will also ensure even and thorough delivery of the plant protection composition onto plant surfaces. Additionally there is the possibility of applying submicron (dry) spraying.

Of course simpler methods of use are open to the end user, and in fact the home gardener will find it desirable to simply dilute the concentrated plant protection composition in a watering can with water and water onto plants via a simple watering can rose.

Regardless of the application approach taken by the end user it is preferred that the plant surfaces to which the plant protection composition is to be applied are well covered by the final diluted composition. Liberal application of the final diluted composition will result in root uptake of the active ingredient of the compositions.

Preferably, in use, 1 -2 litres of the plant protection composition is diluted in 1000 litres of water, per hectare of area to be treated. However, usage and dilution depends on a number of factors, including climate, whether the application is to treat infection or preventative, the type of crop to be treated etc. The present invention will now be described with reference to the accompanying drawings in which: Figure 1 is a chart showing the content of chlorophyll a, chlorophyll b and carotenoid for tomato plants treated with a range of products according to the invention and a current commercial product, each diluted in water and compared with application of water only; Figure 2 is a chart showing peroxidase activity for tomato plants treated with a range of products according to the invention and a current commercial product, each diluted in water and compared with application of water only Figure 3 is a chart showing chitinase activity for tomato plants treated with a range of products according to the invention and a current commercial product, each diluted in water and compared with application of water only; Figure 4 is a chart showing -1,3 glucanase activity for tomato plants treated with a range of products according to the invention and a current commercial product, each diluted in water and compared with application of water only and with reference to the following non-limiting examples.

Example of "minimum" formulation 0 -30 % Coupling agent (Glycerine) o -15 % Wetting agent (Alkyl glucoside) 0.5 -5 % total flavonoid content 1 -10 % total fatty acid content (Caprylic acid) 0 -15 % pH modifier (Citric acid) 98.5-25 % Water (i.e. to make up to 100%) Example of marginally more specific formulation 0 -30 % Coupling agent 0 -15% Wetting agent 1 -10% of bio-mass (of which 0.45-4.5% is flavonoid content) -20 % fatty acid (Caprylic acid) 0 -15 % pH modifier 94-10% Water (i.e. to make up to 100%) Examples of marginally more specific formulation is to be applied are well covered by the final diluted composition. Liberal application of the final diluted composition will result in root up take of the active ingredient of the compositions.

Example of marginally more specific formulation o -30 % Coupling agent o -15 % Wetting agent 1 -10 % of biomass (of which 0.45 -4.5% is flavonoid content) -20 % C8 fatty acid (caprylic acid) o -15 % pH modifier 1 -5 % Ascorbic Acid 93 -5 % Water (i.e. to make up to 100%) Example of marginally more specific formulation 0 -30 % Coupling agent 0 -15 % Wetting agent 1 -10% of biomass (of which 0.45-4.5% isflavonoid content) 5-20 % Caprylic acid 1 -20 % Lactic Acid 93-5% water In a particularly preferred embodiment a plant protection composition was formed with the following ingredients: 10-30% Glycerine (coupling agent) 10-15% Alkyl glucoside (wetting agent to reduce surface tension) 1 -10 % Plant extract biomass 10-20% Food grade organic lactic acid 1 -5 % Ascorbic acid (antioxidant) 10-15 % Vegetable derived free fatty acids -58 % Water There can be other fatty acids of different chain lengths (C8 -C20) used as well as other food grade organic acids, and the proportions of ingredients may have to be varied based on empirical information.

An example formulation is: 2.5% Ascorbic Acid (antioxidant)) 20% Glycerine (coupling agent) 10% Alkyl glucoside (wetting agent) 43% Water 13% Lactic acid monomeric (pH modifier) 8.5% Caprylic acid (Palm kernel oil extract, supplied by KIC International USA) 3.0% Water soluble biomass complex [Of which: 50% Citrus soluble flavonoids (Naringin and Neo-hesperidin) 50% Biomass (pectins, tannins, sugars and minor organic acids)] Example 1 -Demonstration of Antifungal Function The product for use is diluted in water. It was found that when it is required for use against powdery mildew on Arabidopsis thaliana, and against Esca in grapes, dilution in the range of 0.05% to 0.15% (50m1 to 150m1 of product in 100 litres of water) provides a satisfactory dilution.

Glycerine 7.50% Lactic acid 50.0% Caprylic acid (Palm Kernel Oil Extract) 8.5% Bioflavonoids complex 3.0% Ethanol 10.0% Alkyl glycoside 3.0% Ascorbic Acid 3.0% Water 15% Work conducted at Newcastle University has shown that several curative spray applications of the product on Arabidopsis thaliana plants in the laboratory can significantly reduce the amount of powdery mildew (Erysiphe cichoracearum) infection compared to control plants sprayed only with water.

Product Bioflavonoid Complex 3.0% Caprylic acid (Palm Kernel Oil Extract) 22.0% Glycerine 30% Citric Acid 12% Water 33% A product rate of 0.15% in water provided the greatest degree of suppression with an average 93% reduction compared to control plants. Although higher product rates were not tested, it is expected that these would provide an even higher level of control as the 0.15% level of product was able to completely cure plants of powdery mildew infection in several cases. Amy Bilton, M.Phil., University of Newcastle 2009.

Example 2 -Demonstration of Health Maintaining Function Preliminary results from field trial work conducted on wine grapes in Greece showed that over two years, applications of the product at only 0.1% -0.2% by weight diluted in water were sufficient to lead to a significant decrease in acute esca symptoms (apoplexy), while there was a steady decrease in chronic esca symptoms over several growing seasons.

Product Glycerine 7.5% Caprylic acid (Palm kernel oil extract) 8.5% Alkyl glycoside 3.0% Ethanol 10.0% Ascorbic Acid 3.0% Lactic Acid 50.0% Flavonoid Complex 3.0% Water 15% Example 3 -Demonstration of Health Improvement Function -stimulation of multinutrient uptake Tissue analysis conducted on tomato plants has demonstrated that there are increases in the levels of plant macronutrients and micronutrients when treated with the product of Example 2. For example, when tomato plants were treated with the product alone, a 44% increase in protein levels, 40% increase in magnesium levels, and 35% increase in nitrogen levels were recorded over conventional trial plots treated with the grower's usual combination of fungicides, pesticides and fertilizers.

The results are illustrated in Table One below:

Table One

Conventional Product according to Treatment invent/on fungicides, % Variance over pesticides, Con ventional fertilisers.

PROTEIN 10.4% +44% NITROGEN 1.7% +35% CALCIUM 0.25% +12% MAGNESIUM 0.15% +40% PHOSPHORUS 0.6% +8% POTASSIUM 2.7% +4% IRON 8oppm +6% MANGANESE l8ppm +11% COPPER 9ppm +11% ZINC 3oppm +17% BORON l2ppm +33% SULPHUR 0.15% +13%

Example 4

The effect of the addition of differing concentrations of the product in water to tomato seedlings subjected to saline stress in a greenhouse, conducted at the Department of Plant Protection, Faculty of Agriculture, Ege University, Bornova, lzmir, Turkey, was monitored. Application was using hand sprayer as foliar spray of product diluted in litres of water. 4 applications were made at intervals over a 28 day period. The results are disclosed in Table Two. Dry weight in Table Two was measured after oven drying at 70 °C for 3 days.

Product Bioflavanoid complex 3% Caprylic acid (palm kernel oil extract) 22% Citric acid 12% other ingredients including water 63%

Table Two

Root weight (g) Stem Weight (g) Total Length Treatment Fresh Dry Fresh Dry (cm) Control 0.60±0.04 0.07±0.01 0.59±0.10 6.79±0.22 19.32±2.09 (water) lOOmI 1.43±0.07 0.09±0.03 1.76±0.11 8.82±0.34 34.73±3.05 product 75m1 1.37±0.05 0.08±0.02 1.63±0.12 7.84±0.25 32.80±3.12 product 50m1 1.30±0.06 0.08±0.03 1.55±0.11 7.18±0.26 29.93±3.09 product Current 1.42±0.07 0.09±0.04 1.73±0.10 8.90±0.29 35.75±3.09 commercial product X ml s All of the above doses of product treatment significantly increased the root and stem weight and the length of the tomato seedlings as compared to untreated seedlings.

Therefore it can be concluded that the product of the invention has stimulated the nutrient uptake of the tomato seedlings.

Example 5

Photosynthesis efficiency of photosystern II was measured with a portable plant efficiency analyser available from HANSJATECH Inst. Ltd., Norfolk, UK over the 28 day period for the tomato seedling plants of Example 4. Fv/Fm ratios were recorded.

The results are illustrated in Figure One. The Fv/Fm rates were significantly increased for the tomato seedlings to which the product had been added as compared to application of water only.

Example 6

ig of leaf sample of the tomato plants of Example 4 harvested on the 0th, 21st and 701h day of salinity were homogenised with ice-cold 50mM sodium phosphate buffer (pH 7.8) containing 1mM EDTA Na2 and 2% (wlv) insoluble polyvinylpyrrolidone. The homogenates were centrifuged at 13,000g for 20mm at 0°C and supernatants used for determination of enzyme activity. Protein concentration was determined according to Bradford (1976) using bovine serum albumin as a standard. Peroxidase activity was assayed according to Herzog and Fahimi (1973) and the results are in Figure Two. The reaction mixture consisted of 33-diaminobenzidine solution containing 50% (wlv) gelatine and 0.15M Na-phosphate-citrate buffer (pH 4.4) and 0.6% H202.

The increase in absorbance was recorded at 465nm over 3 mins.

Peroxidase is a precursor enzyme that plays an important role in activating plant defence systems to pathogen attack. The best activity for the peroxidase enzyme was observed for seedlings treated with the product.

Both B-1,3 glucanase and chitinase can generate natural plant defence mechanisms to fungal attack by degrading fungal cell wall. B-1,3 glucanase (Figure Three) and chitinase activities (Figure Four) of the tomato plants treated with the product were found to be higher than untreated plants.

Example 7

The effect of adding the product of Example 2 to 500 chicory hypocotyls was investigated and compared to the effect of adding gibberellin acid, utilising the Audus (1972) bioassay method. The results indicate that the product has a gibberellin like activity and hence stimulates growth in the chicory hypocotyls.

Claims

Claims 1. A plant protection composition comprising at least one fatty acid chain of between 2 and 10 carbons in length and flavonoid content.
2. The composition of claim 1, wherein at least one fatty acid chain is an aliphatic fatty acid.
3. The composition of any preceding claim wherein the at least one fatty acid chain is in a straight chain form.
4. The composition of any preceding claim, wherein the at least one fatty acid chain is of between 6 and 10 carbon atoms in length.
5. The composition of claim 4, wherein the fatty acid chain is hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid or decanoic acid.
6. The composition of claim 5, wherein the fatty acid chain is octanoic acid.
7. The composition of any preceding claim, wherein the at least one fatty acid is contained in, or derived from, a triglyceride oil.
8. The composition of claim 7, wherein the triglyceride oil is a naturally occurring triglyceride oil.
9. The composition of claim 8, wherein the naturally occurring triglyceride oil is neem oil, palm kern oil or palm oil.
10. The composition of claim 9, wherein the naturally occurring triglyceride oil is palm oil.
11. The composition of any preceding claim, wherein the flavonoid content comprises a mixture of flavonoid glycosides.
12. The composition of claim 11, wherein the flavonoid glycosides are glycosides of flavanone or glycosides of anthocyanidins.
13. The composition of claim 12,wherein the flavonoid content comprises at least naringen and neohesperidin.
14. The composition of any preceding claim, wherein the flavonoid content further comprises one or more compounds selected from the group of neoeriocitrin, isonaringin, hesperidin, neodiosmin, naringenin, poncirin and rhiofolin.
15. The composition of claims 13 or 14, wherein the flavonoid content comprises at least 25%, at least 40%, at least 50% or at least 65% by weight of naringin.
16. The composition of any of claims 13, 14 or 15, wherein the flavonoid content comprises at least 15%, at least 20%, at least 25% or at least 35% by weight of neohesperidin.
17. The composition of any of claims 13 to 16, wherein the flavonoid content comprises at least 75% of both naringin and neohesperidin.
18. The composition of any preceding claim, wherein the flavonoids are derived from an extract of citrus fruit plants or berry fruit plants.
19. The composition of claim 18 wherein the flavonoids are derived from an extract of bitter oranges.
20. The composition of either of claims 18 or 19, wherein the flavonoid is comprised within biomass.
21. The composition of claim 20, wherein the biomass contains the flavonoids in about 10% to 75% by weight of the total biomass weight.
22. The composition of claim 21, wherein the biomass contains the flavonoids in about 30% to 60% by weight of the total biomass weight.
23. The composition of claim 22, wherein the biomass contains the flavonoids in about 40% to 50% by weight of the total biomass weight.
24. The composition of any preceding claim, further comprising oleuropein or an acetylated derivative thereof.
25. The composition of any preceding claim, further comprising a fruit acid.
26. The composition of claim 25, wherein the fruit acid is citric acid, malic acid or ascorbic acid.
27. The composition of claim 26, wherein the fruit acid is ascorbic acid.
28. The composition of any of claims 25 to 27, wherein the fruit acid to flavonoid ratio is 1:3.
29. The composition of any preceding claim, wherein the plant protection composition is diluted with water to form a diluted composition.
30. The composition of claim 29, wherein the concentration of the plant protection composition is in the range of 0.05 and 0.5% by weight with respect to the diluted composition.
31. The composition of either of claims 29 or 30, wherein the pH of the diluted composition is in the range pH 2.5 to pH 4.
32. The composition of any of preceding claim, wherein the plant protection composition further comprises a chelating agent.
33. The composition of claim 32, wherein the chelating agent is an aliphatic organic acid.
34. The composition of claim 33, wherein the chelating agent is lactic acid or citric acid.
35. The composition of claim 33, wherein the chelating agent is an aromatic organic compound.
36. The composition of claim 35, wherein the chelating agent is salicylic acid.
37. The composition of any preceding claim, wherein the plant protection composition further comprises a nutrient complex providing micro and macro nutrients.
38. The composition of any preceding claim, wherein the plant protection composition further comprises a coupling agent with a hydrophilic-lipophilic balance value of approximately 7.
39. The composition of claim 38, wherein the coupling agent is fulvic acid, glycerine or ethyl alcohol.
40. The composition of any preceding claim, wherein the plant protection composition further comprises a surfactant.
41. The composition of claim 40, wherein the surfactant is an alkyl glucoside.
42. The composition of claim 1, consisting of: 0-30% coupling agent 0-15% surfactant 0.5-5% total flavonoid content 1-10% total fatty acid content 0-15% pH modifier 98.5-25% water
43. Use of a plant protection composition as defined in any of claims ito 42 as a plant treatment agent to restore and/or maintain plant health in response to pathogenic aftack.
44. Use of a plant protection composition as defined in any of claims 1 to 42 in agriculture, horticulture or home gardening as an anti-fungal agent.
45. Use of a plant protection composition as defined in any of claims 1 to 42 in agriculture, horticulture or home gardening as an anti-fungal agent and antioxidant agent.
46. Use of a plant protection composition as defined in any of claims 1 to 42 in agriculture, horticulture or home gardening as an anti-fungal and antibacterial treatment, alone or in combination with an antioxidant agent.
47. Use of a plant protection composition as defined in any of claims ito 42 as a plant treatment agent to stimulate multi nutrient uptake of plants.48 A method of producing a metastable micro emulsion comprising the steps of adding the components of the plant protection composition of any one of claims 1 to 42 into a high shear mixer whilst mixing at a high shear rate.49. The method of claim 48, where any coupling agent is added first and subjected to high shear mixing prior to the addition of further components.50. The method of claim 49, where any surfactant is added after high shear mixing of the coupling agent and prior to the addition of further components.51. A method of applying a plant protection composition as defined in any one of claims 1 to 42 to plants or post harvest food stock by means of spraying, fogging or as a process wash.52. The method of claim 51, wherein a first step comprises diluting the plant protection composition with dilution water.53. The method of claim 52, wherein the concentration of the plant protection composition is in the range of 0.05 and 0.5% by weight with respect to the diluted composition.54. The method of either of claims 52 or 53, wherein the dilution water is mixed with the plant protection composition in a spray tank prior to spraying.55. The method of any of claims 51 to 54, wherein an electrostatic sprayer is employed for spraying.