Natural deep eutectic systems

Abstract

This invention generally relates to a deep eutectic system (DES) formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoic acid is present in a gymnosperm exudate. More specifically, but not exclusively, it relates to a DES formed from a hydroxylated terpenoid such as menthol or thymol, and a terpenoic acid present in pine rosin, such as abietic acid. Biofouling control, antimicrobial, horticultural, viticultural, and arthropod and / or pest control compositions comprising the DES are also provided, as are compositions for releasing a volatile compound.

Description

[0001] NATURAL DEEP EUTECTIC SYSTEMS

[0002] Field of the invention

[0003] This invention generally relates to a deep eutectic system (DES) formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoic acid is present in a gymnosperm exudate. More specifically, but not exclusively, it relates to a non-ionic DES formed from a hydroxylated monoterpenoid such as menthol or thymol, and a terpenoic acid present in pine rosin, such as abietic acid. Compositions for releasing terpenoids into air, into water, and surfaceactive compositions are provided. Biofouling control compositions, antimicrobial compositions, horticultural compositions, viticultural compositions, and arthropod and / or pest control compositions comprising the DES are also provided.

[0004] Background to the invention

[0005] Terpenoids are a large and highly diverse set of plant compounds with a wide range of potentially useful properties. However, terpenoids are typically highly volatile, and this limits their usefulness.

[0006] Terpenoids exposed to air may volatilise rapidly, producing a higher than desired initial concentration of the terpenoid in the air. This initial high concentration is often followed by a sharp decrease once the majority of the terpenoid has been volatilised, leading to little sustained release. Similarly, in aquatic applications, terpenoids may dissolve too rapidly. This again produces a high initial release followed by a rapid drop-off, with little sustained release.

[0007] In many applications, it would be desirable to have terpenoids released over a longer timeframe. To extend the duration of effect, it may be desirable to increase the initial concentration of terpenoid applied; however as noted above, this may lead to an undesirably high initial concentration. Alternatively, lower concentrations of terpenoids could be applied at regular intervals, however this is inconvenient and may be impractical in many applications.

[0008] Furthermore, terpenoids are often brittle solids at room temperature, which can make it difficult to apply them to surfaces.

[0009] It is desirable to provide terpenoid-comprising compositions with moderated, delayed, and / or extended release of the terpenoid. It is particularly desirable to provide terpenoid-comprising compositions wherein the release of terpenoids may be adjusted depending on the desired application. It is also desirable to provide terpenoid-comprising compositions having a viscosity that may be adjusted depending on the desired application.

[0010] It is also desirable to provide compositions and methods for releasing a volatile compound into air, or for releasing a compound into water.

[0011] Biofouling is a major problem for the maritime industry, costing the sector about US$100 billion annually and leading to overall economic costs of over US$150 billion. These include costs for cleaning, drydocking, re-painting, and increases in fuel usage due to increased drag.

[0012] Chemical antifoul coatings are often used to prevent or reduce the accumulation of biofouling, however these can accumulate in marine organisms and cause serious damage to marine ecosystems. Tributyltin (TBT) was banned as an antifouling agent by the International Maritime Organization in 2008, and copper and other biocides are starting to be banned in some territories due to concerns about environmental damage and biological persistence.

[0013] It is also desirable to provide biofouling control compositions with reduced environmental impact, low or no environmental persistence, and / or no bioaccumulation. It is particularly desirable to provide such biofouling control compositions formed from natural components.

[0014] Plants that have been wounded, for example by pruning or harvesting, are often vulnerable to infection by mircroorganisms such as Eutypha and Botryosphereia. For example, in New Zealand these diseases are estimated to reduce the profitability of vineyards by approximately 14%. Several products for plant wound management exist, however they are expensive and often contain chemical fungicides, which may be undesirable.

[0015] It is also desirable to provide horticultural and / or viticultural compositions. It is particularly desirable to provide such compositions formed from natural components.

[0016] Pests, particularly arthropod pests (such as moths and mites), are often a problem for agriculture, apiculture, and storage of crops. While pesticides may be used, many insects are becoming resistant to widely-used insecticides, and there remain concerns about off-target effects (for example, to honeybees) and environmental persistence.

[0017] It is also desirable to provide arthropod and / or pest control compositions. It is particularly desirable to provide such compositions formed from natural components. Food borne illnesses can lead to loss of productivity, medical costs, and even death. Food processing facilities must maintain rigorous food safety standards to minimise the risk of contamination. Likewise, hospitals, doctors offices, and other medical facilities must maintain high standards of cleanliness to avoid infection or transmission of microbial pathogens.

[0018] It is also desirable to provide antimicrobial compositions, such as antibacterial, antifungal, and / or antiviral compositions. It is particularly desirable to provide such compositions formed from natural components.

[0019] It is an object of the invention to go some way towards meeting one or more of these desiderata, or at least to provide the public with a useful choice.

[0020] In this specification where reference has been made to patent specifications, other external documents, or other sources of information, this is generally for the purpose of providing a context for discussing the features of the invention. Unless specifically stated otherwise, reference to such external documents is not to be construed as an admission that such documents, or such sources of information, in any jurisdiction, are prior art, or form part of the common general knowledge in the art.

[0021] Summary of the invention

[0022] In a first aspect, the invention provides a deep eutectic system (DES) formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoic acid is present in a gymnosperm exudate.

[0023] In a second aspect, the invention provides a method of producing the DES of the first aspect, the method comprising contacting at least one terpenoid and a. at least one terpenoic acid that is present in a gymnosperm exudate; and / or b. at least one resin acid; to produce the DES.

[0024] In a third aspect, the invention provides a composition comprising the DES of the first aspect and at least one additional component. In a fourth aspect, the invention provides a biofouling control composition comprising, consisting essentially of, or consisting of the DES of the first aspect, or the composition of the third aspect.

[0025] In a fifth aspect, the invention provides a watercraft, structure, or article to which the biofouling control composition of the fourth aspect has been applied.

[0026] In a sixth aspect, the invention provides a method of controlling biofouling of a surface, the method comprising applying the composition of the fourth aspect to the surface.

[0027] In a seventh aspect, the invention provides an antimicrobial composition, such as an antibacterial, antifungal, and / or antiviral composition, comprising, consisting essentially of, or consisting of the DES of the first aspect, or the composition of the third aspect.

[0028] In an eighth aspect, the invention provides a method of reducing or preventing microbial growth or survival on a surface, the method comprising applying the composition of the seventh aspect to the surface.

[0029] In a ninth aspect, the invention provides a horticultural and / or viticultural composition comprising, consisting essentially of, or consisting of the DES of the first aspect, or the composition of the third aspect.

[0030] In a tenth aspect, the invention provides a method of improving healing of a plant wound, the method comprising applying the composition of the ninth aspect to the plant wound.

[0031] In an eleventh aspect, the invention provides a method of preventing, or reducing the likelihood and / or severity of, infection in a plant, the method comprising applying the composition of the ninth aspect to the plant or part thereof.

[0032] In a twelfth aspect, the invention provides a method of preventing or reducing the risk or severity of pest damage to a plant (such as insect pest damage), the method comprising applying the composition of the ninth aspect to the plant or part thereof.

[0033] In a thirteenth aspect, the invention provides a method of controlling a plant pest, the method comprising applying the composition of the ninth aspect to the plant or part thereof. In a fourteenth aspect, the invention provides a composition for releasing a volatile compound into air, the composition comprising, consisting essentially of, or consisting of the DES of the first aspect, or the composition of the third aspect.

[0034] In a fifteenth aspect, the invention provides a method of releasing a volatile compound into air, the method comprising contacting the composition of the fourteenth aspect, and the air.

[0035] In a sixteenth aspect, the invention provides a composition for releasing a compound into water, the composition comprising, consisting essentially of, or consisting of the DES of the first aspect, or the composition of the third aspect.

[0036] In a seventeenth aspect, the invention provides a method of releasing a compound into water, the method comprising contacting the composition of the sixteenth aspect, and water.

[0037] In an eighteenth aspect, the invention provides an arthropod control composition comprising, consisting essentially of, or consisting of the DES of the first aspect, or the composition of the third aspect.

[0038] In a nineteenth aspect, the invention provides a method of controlling arthropods in a treatment area, the method comprising applying the composition of the eighteenth aspect to the treatment area.

[0039] In a twentieth aspect, the invention provides a pest control composition comprising, consisting essentially of, or consisting of the DES of the first aspect, or the composition of the third aspect.

[0040] In a twenty-first aspect, the invention provides a method of controlling a pest in a treatment area, the method comprising applying the composition of the twentieth aspect to the treatment area.

[0041] In a twenty-second aspect, the invention provides a deep eutectic system (DES) formed from at least one terpenoid and a gymnosperm exudate (preferably a conifer exudate, more preferably pine rosin) comprising at least one terpenoic acid.

[0042] In a twenty-third aspect, the invention provides a deep eutectic system (DES) formed from at least one terpenoid and a gymnosperm exudate (preferably a conifer exudate, more preferably pine rosin) comprising at least two terpenoic acids. In a twenty-fourth aspect, the invention provides a method of producing the DES of aspect 22 or 23, the method comprising contacting the at least one terpenoid and the gymnosperm exudate, to produce the DES.

[0043] In a twenty-fifth aspect, the invention provides a composition comprising the DES of aspect 22 or 23 and at least one additional component.

[0044] In a twenty-sixth aspect, the invention provides a method of functionalising a gymnosperm exudate (preferably pine rosin), the method comprising contacting at least one terpenoid and a gymnosperm exudate comprising at least one terpenoic acid, such that the at least one terpenoid and the at least one terpenoic acid form non-ionic, non-covalent intermolecular interactions.

[0045] In a twenty-seventh aspect, the invention provides a method of modifying a property of a gymnosperm exudate (preferably pine rosin), the method comprising contacting at least one terpenoid and a gymnosperm exudate comprising at least one terpenoic acid, such that the at least one terpenoid and the at least one terpenoic acid form non-ionic, non-covalent intermolecular interactions; wherein the property is selected from: a. viscosity, b. hydrophobicity, c. bioactivity, d. rate of release of the at least one terpenoid to air, e. rate of release of the at least one terpenoid to water, or f. any combination of any two or more of a to e.

[0046] In a twenty-eighth aspect, the invention provides a functionalised or modified gymnosperm exudate prepared by either of the two preceding aspects.

[0047] In a twenty-ninth aspect, the invention provides a functionalised gymnosperm exudate comprising: a. a gymnosperm exudate comprising at least one terpenoic acid; and b. at least one terpenoid; wherein the at least one terpenoic acid and the at least one terpenoid form non-ionic, non- covalent intermolecular interactions.

[0048] In a thirtieth aspect, the invention provides a biofouling control composition comprising, consisting essentially of, or consisting of the DES of aspect 22 or 23, the composition of aspect 25, or the functionalised or modified gymnosperm exudate of aspect 28 or 29.

[0049] In a thirty-first aspect, the invention provides a watercraft, structure, or article to which the biofouling control composition of aspect 30 has been applied.

[0050] In a thirty-second aspect, the invention provides a method of controlling biofouling of a surface, the method comprising applying the composition of aspect 30 to the surface.

[0051] In a thirty-third aspect, the invention provides an antimicrobial composition, such as an antibacterial, antifungal, and / or antiviral composition, comprising, consisting essentially of, or consisting of the DES of the aspect 22 or 23, the composition of aspect 25, or the functionalised or modified gymnosperm exudate of aspect 28 or 29.

[0052] In a thirty-fourth aspect, the invention provides a method of reducing or preventing microbial growth or survival on a surface, the method comprising applying the composition of aspect 33 to the surface.

[0053] In a thirty-fifth aspect, the invention provides a horticultural and / or viticultural composition comprising, consisting essentially of, or consisting of the DES of aspect 22 or 23, the composition of aspect 25, or the functionalised or modified gymnosperm exudate of aspect 28 or 29.

[0054] In a thirty-sixth aspect, the invention provides a method of improving healing of a plant wound, the method comprising applying the composition of aspect 35 to the plant wound.

[0055] In a thirty-seventh aspect, the invention provides a method of preventing, or reducing the likelihood and / or severity of, infection in a plant, the method comprising applying the composition of aspect 35 to the plant or part thereof. In a thirty-eighth aspect, the invention provides a method of preventing or reducing the risk or severity of pest damage to a plant (such as insect pest damage), the method comprising applying the composition of aspect 35 to the plant or part thereof.

[0056] In a thirty-ninth aspect, the invention provides a method of controlling a plant pest, the method comprising applying the composition of aspect 35 to the plant or part thereof.

[0057] In a fortieth aspect, the invention provides a composition for releasing a volatile compound into air, the composition comprising, consisting essentially of, or consisting of the DES of aspect 22 or 23, the composition of aspect 25, or the functionalised or modified gymnosperm exudate of aspect 28 or 29.

[0058] In a forty-first aspect, the invention provides a method of releasing a volatile compound into air, the method comprising contacting the composition of aspect 40, and the air.

[0059] In a forty-second aspect, the invention provides a composition for releasing a compound into water, the composition comprising, consisting essentially of, or consisting of the DES of aspect 22 or 23, the composition of aspect 25, or the functionalised or modified gymnosperm exudate of aspect 28 or 29.

[0060] In a forty-third aspect, the invention provides a method of releasing a compound into water, the method comprising contacting the composition of aspect 42, and water.

[0061] In a forty-fourth aspect, the invention provides an arthropod control composition comprising, consisting essentially of, or consisting of the DES of aspect 22 or 23, the composition of aspect 25, or the functionalised or modified gymnosperm exudate of aspect 28 or 29.

[0062] In a forty-fifth aspect, the invention provides a method of controlling arthropods in a treatment area, the method comprising applying the composition of aspect 44 to the treatment area.

[0063] In a forty-sixth aspect, the invention provides a Varroa mite control composition comprising, consisting essentially of, or consisting of the DES of aspect 1, 22, or 23, the composition of aspect 3 or 25, or the functionalised or modified gymnosperm exudate of aspect 28 or 29.

[0064] In a forty-seventh aspect, the invention provides a method of controlling Varroa mites in a treatment area, the method comprising applying the composition of aspect 46 to the treatment area. In a forty-eighth aspect, the invention provides a pest control composition comprising, consisting essentially of, or consisting of the DES of aspect 22 or 23, the composition of aspect 25, or the functionalised or modified gymnosperm exudate of aspect 28 or 29.

[0065] In a forty-ninth aspect, the invention provides a method of controlling a pest in a treatment area, the method comprising applying the composition of aspect 48 to the treatment area.

[0066] In a fiftieth aspect, the invention provides a hoof and / or horn protecting composition comprising, consisting essentially of, or consisting of the DES of aspect 22 or 23, the composition of aspect 25, or the functionalised or modified gymnosperm exudate of aspect 28 or 29.

[0067] In a fifty-first aspect, the invention provides a method of treating, reducing the risk of, or preventing an infection of hoof and / or horn, the method comprising applying the DES of aspect 22 or 23, the composition of aspect 25 or 50, or the functionalised or modified gymnosperm exudate of aspect 28 or 29, to the hoof and / or horn of an animal in need thereof.

[0068] In a further aspect, the invention provides use of the DES of aspect 22 or 23, the composition of aspect 25 or 50, or the functionalised or modified gymnosperm exudate of aspect 28 or 29, in the manufacture of a medicament for treating, reducing the risk of, or preventing infection of hoof and / or horn of an animal in need thereof.

[0069] In a further aspect, the invention provides a method of treating, reducing the risk of, or preventing a topical infection, the method comprising applying the DES of aspect 22 or 23, the composition of aspect 25, or the functionalised or modified gymnosperm exudate of aspect 28 or 29, to a subject in need thereof.

[0070] In a further aspect, the invention provides use of the DES of aspect 22 or 23, the composition of aspect 25, or the functionalised or modified gymnosperm exudate of aspect 28 or 29, in the manufacture of a medicament for treating, reducing the risk of, or preventing a topical infection.

[0071] Any of the following embodiments, alone or in any combination, may apply to any one or more of the above aspects.

[0072] In some embodiments, the at least one terpenoic acid comprises at least one resin acid, preferably a diterpenoic acid, more preferably abietic acid or an isomer or derivative thereof. In some embodiments, the at least one terpenoic acid is derived from 1, 2, 3, 4, 5, 6, 7, 8, or more isoprene units, preferably from 3, 4, or 5 isoprene units, more preferably from 4 isoprene units. In some embodiments, the at least one terpenoic acid is a hemiterpenoic acid, monoterpenoic acid, sesquiterpenoic acid, diterpenoic acid, sesterterpenoic acid, triterpenoic acid, tetraterpenoic acid, or polyterpenoic acid; preferably a diterpenoic acid. In a specifically contemplated embodiment, the at least one terpenoic acid is a monocarboxylated diterpenoic acid (i.e. a diterpenoid having a single carboxylic acid group).

[0073] In some embodiments, the at least one terpenoic acid is non-volatile. In some embodiments the at least one terpenoic acid has a vapour pressure of less than about 0.2 mmHg at 25°C, such as less than about 0.18, less than about 0.16, less than about 0.14, less than about 0.12, less than about 0.1, less than about 0.08, less than about 0.06, less than about 0.04, less than about 0.02, less than about 0.01, less than about 0.005, or about 0 mmHg at 25°C, and useful ranges may be selected between any of these values (for example, from about 0 to about 0.2, from about 0 to about 0.18, from about 0 to about 0.16, from about 0 to about 0.14, from about 0 to about 0.12, from about 0 to about 0.1, from about 0 to about 0.08, from about 0 to about 0.06, from about 0 to about 0.04, from about 0 to about 0.02, from about 0 to about 0.01, or from about 0 to about 0.005).

[0074] In some embodiments, the at least one terpenoic acid has a melting point of at least about 25°C, such as at least about 50°C, at least about 100°C, at least about 120°C, at least about 140°C, at least about 160°C, at least about 180°C, at least about 200°C, at least about 220°C, at least about 240°C, at least about 260°C, at least about 280°C, at least about 300°C, at least about 320°C, at least about 340°C, or at least about 360°C, and useful ranges may be selected between any of these values (for example, from about 25°C to about 360°C, from about 50°C to about 360°C, from about 100°C to about 360°C, from about 100°C to about 320°C, from about 100°C to about 280°C, from about 100°C to about 240°C, from about 100°C to about 200°C, from about 120°C to about 360°C, from about 120°C to about 320°C, from about 120°C to about 280°C, from about 120°C to about 240°C, from about 120°C to about 200°C, from about 140°C to about 360°C, from about 140°C to about 320°C, from about 140°C to about 280°C, from about 140°C to about 240°C, from about 140°C to about 200°C, from about 160°C to about 360°C, from about 160°C to about 320°C, from about 160°C to about 280°C, from about 160°C to about 240°C, or from about 160°C to about 200°C). In some embodiments, the at least one terpenoic acid is selected from the group consisting of abietic acid, betulinic acid, fencholic acid, moronic acid, oleanolic acid, ursolic acid, and isomers or derivatives thereof.

[0075] In some embodiments, the gymnosperm exudate is a conifer exudate, preferably pine rosin. In some embodiments, the at least one terpenoic acid is present in, or provided by, tall oil. In some embodiments, the at least one terpenoic acid is present in, or provided by, gum rosin. In some embodiments, the at least one terpenoic acid is present in, or provided by, wood rosin. In some embodiments, the at least one terpenoic acid is present in, or provided by, tall oil, gum rosin, and / or wood rosin.

[0076] In some embodiments, the DES comprises two or more compounds present in a gymnosperm exudate. In some embodiments the gymnosperm exudate, conifer exudate, pine rosin, or tall oil is used to form a DES without prior refinement, or with minimal refinement. In some embodiments, the DES comprises two or more compounds present in a gymnosperm exudate, conifer exudate, pine rosin, or tall oil, preferably two or more compounds selected from resin acids such as abietic acid and its isomers, fatty acids, fatty alcohols, and sterols.

[0077] In some embodiments, the gymnosperm exudate, conifer exudate, or pine rosin comprises at least about 30% by weight of one or more resin acids (such as abietic acid and structural analogues), such as at least about 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or at least about 90%, and useful ranges may be selected between any of these values (for example, from about 30% to about 90%, from about 30% to about 80%, from about 30% to about 70%, from about 40% to about 90%, from about 40% to about 80%, from about 40% to about 70%, from about 50% to about 90%, from about 50% to about 80%, from about 50% to about 70%, from about 60% to about 90%, from about 60% to about 80%, or from about 60% to about 70%).

[0078] In some embodiments, the gymnosperm exudate, conifer exudate, or pine rosin comprises at least about 30% by weight of abietic acid, such as at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, and useful ranges may be selected between any of these values (for example, from about 30% to about 80%, from about 35% to about 80%, from about 35% to about 70%, from about 35% to about 60%, from about 35% to about 50%, from about 40% to about 80%, from about 40% to about 70%, from about 40% to about 60%, from about 40% to about 50%, from about 45% to about 80%, from about 45% to about 70%, from about 45% to about 60%, from about 45% to about 50%, from about 50% to about 80%, from about 50% to about 70%, or from about 50% to about 60%).

[0079] In some embodiments, the at least one terpenoid comprises an oxygenated terpenoid, more preferably a hydroxylated terpenoid, most preferably a monohydroxylated terpenoid. In some embodiments, the at least one terpenoid comprises a monoterpenoid, preferably a hydroxylated monoterpenoid, most preferably a monohydroxylated monoterpenoid.

[0080] In some embodiments, the terpenoid is derived from 1, 2, 3, 4, 5, 6, 7, 8, or more isoprene units, preferably from 1, 2, 3, or 4 isoprene units, more preferably from 2 isoprene units. In some embodiments, the terpenoid is a hemiterpenoid, monoterpenoid, sesquiterpenoid, diterpenoid, sesterterpenoid, triterpenoid, tetraterpenoid, or polyterpenoid; preferably a hemiterpenoid, monoterpenoid, sesquiterpenoid, or diterpenoid; more preferably a monoterpenoid.

[0081] In some embodiments, the terpenoid is acyclic, monocyclic, bicyclic, tricyclic, or tetracyclic, or polycyclic; preferably monocyclic.

[0082] In some embodiments, the terpenoid is a volatile compound. In some embodiments, the terpenoid has a vapour pressure of at least about 0.001 mmHg at 25°C, such as at least about 0.002, at least about 0.003, at least about 0.004, at least about 0.005, at least about 0.006, at least about 0.007, at least about 0.008, at least about 0.009, at least about 0.01, at least about 0.015, at least about 0.02, at least about 0.03, at least about 0.04, at least about 0.05, at least about 0.06, at least about 0.07, at least about 0.08, at least about 0.09, at least about 0.1, or at least about 0.2, and useful ranges may be selected between any of these values (for example, from about 0.001 to about 0.2, from about 0.001 to about 0.1, from about 0.001 to about 0.09, from about 0.001 to about 0.08, from about 0.001 to about 0.07, from about 0.01 to about 0.2, from about 0.01 to about 0.1, from about 0.01 to about 0.09, from about 0.01 to about 0.08, from about 0.01 to about 0.07, from about 0.015 to about 0.2, from about 0.015 to about 0.1, from about 0.015 to about 0.09, from about 0.015 to about 0.08, or from about 0.015 to about 0.07).

[0083] In some embodiments, the terpenoid is solid at room temperature (for example, at 25°C). In some embodiments, the terpenoid has a melting point of at least about 25°C, such as at least about 26°C, at least about 27°C, at least about 28°C, at least about 29°C, at least about 30°C, at least about 31°C, at least about 32°C, at least about 33°C, at least about 34°C, at least about 35°C, at least about 36°C, at least about 37°C, at least about 38°C, at least about 39°C, at least about 40°C, at least about 41°C, at least about 42°C, at least about 43°C, at least about 44°C, at least about 45°C, at least about 46°C, at least about 47°C, at least about 48°C, at least about 49°C, at least about 50°C, at least about 51°C, at least about 52°C, at least about 53°C, at least about 54°C, at least about 55°C, at least about 56°C, at least about 57°C, at least about 58°C, at least about 59°C, or at least about 60°C, and useful ranges may be selected between any of these values (for example, from about 25°C to about 60°C, from about 25°C to about 56°C, from about 25°C to about 52°C, from about 27°C to about 60°C, from about 27°C to about 56°C, from about 27°C to about 52°C, from about 29°C to about 60°C, from about 29°C to about 56°C, from about 29°C to about 52°C, from about 31°C to about 60°C, from about 31°C to about 56°C, from about 31°C to about 52°C, from about 33°C to about 60°C, from about 33°C to about 56°C, from about 33°C to about 52°C, from about 35°C to about 60°C, from about 35°C to about 56°C, or from about 35°C to about 52°C).

[0084] In some embodiments, the at least one additional component is selected from the group consisting of a binder, a diluent, a preservative, a viscosity-modifying agent, or an active agent. In some embodiments, the at least one additional component is selected from the group consisting of paraffin, beeswax, propolis, and essential oils and extracts from plants, preferably plants of the Rosaceae, Lamiaceae, Apiaceae, Winteraceae, Asteraceae, Schisandraceae, Lauraceae, Geraniaceae, and / or Myrtaceae families. In some embodiments, the active agent is selected from the group consisting of an antifouling agent; an antimicrobial agent such as an antibacterial, antifungal, and / or antiviral agent; and an arthropod (such as an insect and / or arachnid) control agent such as an arthropod repellent and / or an arthropodicidal agent.

[0085] In some embodiments, the at least one terpenoid comprises a biofouling control compound. In some embodiments, the composition is a biofouling control composition.

[0086] In some embodiments, the at least one terpenoid comprises an antimicrobial compound, such as an antibacterial, antifungal, and / or antiviral compound. In some embodiments, the composition is an antimicrobial composition, such as an antibacterial, antifungal, and / or antiviral composition. In some embodiments, the at least one terpenoid is selected from the group consisting of aethiopinone, borneol, bornyl acetate, isoborneol, camphor, carvacrol, dihydrocarveol, (+)-carvone, 1,8-cineole, citral, eucalpytol, eugenol, farnesol, geraniol, geranyl acetate, (+)-limonene, (±)- linalool, menthol, menthone, nerol, perillyl alcohol, oc-pinene, (+)-|3-pinene, salvipisone, (+)- terpinen-4-ol, oc-terpinoel, (-)-thujone, thymol, xanthorrhizol, and derivatives and isomers thereof. In some embodiments, the composition is a horticultural and / or viticultural composition. In some embodiments, the composition is a horticultural and / or viticultural wound dressing composition. In some embodiments, the composition is a plant pest control composition.

[0087] In some embodiments, the plant is a vine, such as a grape vine. In some embodiments the plant is a food crop plant, fodder plant, forage plant, ornamental plant, or a plant grown for biomass.

[0088] In some embodiments, the at least one terpenoid comprises a volatile compound. In some embodiments, the volatile compound is a scent compound. In some embodiments, the composition is a fragrance-releasing composition. In some embodiments, the at least one terpenoid is selected from the group consisting of camphor, 1,8-cineole, carvone, citral, citronellal, citronellol, eucalyptol, eugenol, geraniol, geranyl acetatejasmone, limonene, linalool, linalyl acetate, oc-lonone, menthol, nerol, nerolidol, ocimene, terpineol, thujone, thymol, and derivatives and isomers thereof.

[0089] In some embodiments, the volatile compound is a pest repellent compound. In some embodiments, the pest is an arthropod pest, preferably an insect pest and / or an arachnid pest. In some embodiments, the at least one terpenoid is selected from the group consisting of borneol, iso borneol, borynl acetate, iso borynl acetate, camphor, carvone, citronellal, citronellol, eucalyptol, fencholic acid, a- and p-terpinol, and linalool, and derivatives thereof.

[0090] In some embodiments, the composition is an arthropod control composition. In some embodiments, the arthropod is an arthropod pest. In some embodiments, the arthropod is an insect and / or an arachnid.

[0091] In some embodiments, the molar ratio of the at least one terpenoid to the at least one terpenoic acid, or the ratio of hydrogen bond donating groups to hydrogen bond accepting groups, is from about 6:1 to about 1:6, such as from about 6:1 to about 1:5, from about 6:1 to about 1:4, from about 6:1 to about 1:3, from about 6:1 to about 1:2, from about 6:1 to about 1:1, from about 5:1 to about 1:6, from about 5:1 to about 1:5, from about 5:1 to about 1:4, from about 5:1 to about 1:3, from about 5:1 to about 1:2, from about 5:1 to about 1:1, from about 4:1 to about 1:6, such as from about 4:1 to about 1:5, from about 4:1 to about 1:4, from about 4:1 to about 1:3, from about 4:1 to about 1:2, from about 4:1 to about 1:1, from about 3:1 to about 1:6, such as from about 3:1 to about 1:5, from about 3:1 to about 1:4, from about 3:1 to about 1:3, from about 3:1 to about 1:2, from about 3:1 to about 1:1, from about 2:1 to about 1:6, such as from about 2:1 to about 1:5, from about 2:1 to about 1 :4, from about 2:1 to about 1:3, from about 2:1 to about 1 :2, from about 2:1 to about 1 :1, from about 1 :1 to about 1 :6, such as from about 1 :1 to about 1:5, from about 1 :1 to about 1 :4, from about 1:1 to about 1 :3, from about 1 :1 to about 1 :2, or about 1 :1.

[0092] In some embodiments, the melting point of the DES is at least about 1 °C lower than the melting point of one or more components of the DES (preferably at least about 1°C lower than each component of the DES), such as at least about 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 12°C, 14°C, 16°C, 18°C, 20°C, 22°C, 24°C, 26°C, 28°C, 30°C, 35°C, 40°C, 45°C, or at least about 50°C lower than the melting point of one or more components of the DES (preferably than each component of the DES).

[0093] In some embodiments, the DES has a melting point of less than about 60°C, such as less than about 58°C, less than about 56°C, less than about 55°C, less than about 54°C, less than about 52°C, less than about 50°C, less than about 48°C, less than about 46°C, less than about 45°C, less than about 44°C, less than about 42°C, less than about 40°C, less than about 38°C, less than about 36°C, less than about 35°C, less than about 34°C, less than about 32°C, less than about 30°C, less than about 28°C, less than about 26°C, less than about 25°C, less than about 24°C, less than about 22°C, less than about 20°C, less than about 18°C, less than about 16°C, less than about 15°C, less than about 14°C, less than about 12°C, less than about 10°C, less than about 8°C, less than about 6°C, less than about 5°C, less than about 4°C, less than about 2°C, less than about 0°C, less than about - 10°C, less than about -20°C, less than about -30°C, less than about -40°C, less than about -50°C, less than about -60°C, less than about -70°C, less than about -80°C, less than about -90°C, or less than about -100°C, and useful ranges may be selected between any of these value (for example, from about -100°C to about 60°C, from about -100°C to about 55°C, from about -100°C to about 50°C, from about -100°C to about 45°C, from about -100°C to about 40°C, from about -100°C to about 35°C, from about -100°C to about 30°C, from about -100°C to about 25°C, from about -50°C to about 60°C, from about -50°C to about 55°C, from about -50°C to about 50°C, from about -50°C to about 45°C, from about -50°C to about 40°C, from about -50°C to about 35°C, from about -50°C to about 30°C, from about -50°C to about 25°C, from about -20°C to about 60°C, from about -20°C to about 55°C, from about -20°C to about 50°C, from about -20°C to about 45°C, from about -20°C to about 40°C, from about -20°C to about 35°C, from about -20°C to about 30°C, from about -20°C to about 25°C, from about 0°C to about 60°C, from about 0°C to about 55°C, from about 0°C to about 50°C, from about 0°C to about 45°C, from about 0°C to about 40°C, from about 0°C to about 35°C, from about 0°C to about 30°C, from about 0°C to about 25°C, from about 5°C to about 60°C, from about 5°C to about 55°C, from about 5°C to about 50°C, from about 5°C to about 45°C, from about 5°C to about 40°C, from about 5°C to about 35°C, from about 5°C to about 30°C, from about 5°C to about 25°C, from about 10°C to about 60°C, from about 10°C to about 55°C, from about 10°C to about 50°C, from about 10°C to about 45°C, from about 10°C to about 40°C, from about

[0094] 10°C to about 35°C, from about 10°C to about 30°C, from about 10°C to about 25°C, from about

[0095] 15°C to about 60°C, from about 15°C to about 55°C, from about 15°C to about 50°C, from about

[0096] 15°C to about 45°C, from about 15°C to about 40°C, from about 15°C to about 35°C, from about

[0097] 15°C to about 30°C, from about 15°C to about 25°C, from about 20°C to about 60°C, from about

[0098] 20°C to about 55°C, from about 20°C to about 50°C, from about 20°C to about 45°C, from about

[0099] 20°C to about 40°C, from about 20°C to about 35°C, from about 20°C to about 30°C, or from about 20°C to about 25°C).

[0100] In some embodiments, the viscosity of the DES is from about 100 mPa-s to about 1,000,000 mPa-s for Newtonian fluids within the temperature range of -10 - 60°C, preferably at 20°C. Preferably, the viscosity of the DES is from about 100 to about 1,000,000 mPa-s at a temperature of about 20°C, such as from about 500 to about 1000000, from about 500 to about 750000, from about 500 to about 500000, from about 500 to about 100000, from about 500 to about 50000, from about 1000 to about 1000000, from about 1000 to about 750000, from about 1000 to about 500000, from about 1000 to about 100000, from about 1000 to about 50000, from about 5000 to about 1000000, from about 5000 to about 750000, from about 5000 to about 500000, from about 5000 to about 100000 from about 5000 to about 50000, from about 10000 to about 1000000, from about 10000 to about 750000, from about 10000 to about 500000, from about 10000 to about 100000, from about 10000 to about 50000, from about 20000 to about 1000000, from about 20000 to about 750000, from about 20000 to about 500000, from about 20000 to about 100000, from about 20000 to about 50000, from about 30000 to about 1000000, from about 30000 to about 750000, from about 30000 to about 500000, from about 30000 to about 100000, from about 30000 to about 50000, from about 40000 to about 1000000, from about 40000 to about 750000, from about 40000 to about 500000, from about 40000 to about 100000, from about 40000 to about 50000, from about 50000 to about 1000000, from about 50000 to about 750000, from about 50000 to about 500000, or from about 50000 to about 100000 mPa-s.

[0101] In some embodiments, the viscosity of the DES is from about 1 mPa-s to about 500,000 mPa-s for non-Newtonian fluids within the temperature range of -10 - 60°C (preferably at 20°C), over the shear rate of 0.1 - 10,000 s’1, such as from about 100 to about 500000, from about 100 to about 400000, from about 100 to about 300000, from about 100 to about 200000, from about 100 to about 100000, from about 1000 to about 500000, from about 1000 to about 400000, from about 1000 to about 300000, from about 1000 to about 200000, from about 1000 to about 100000, from about 10000 to about 500000, from about 10000 to about 400000, from about 10000 to about 300000, from about 10000 to about 200000, from about 10000 to about 100000, from about 20000 to about 500000, from about 20000 to about 400000, from about 20000 to about 300000, from about 20000 to about 200000, from about 20000 to about 100000, from about 30000 to about 500000, from about 30000 to about 400000, from about 30000 to about 300000, from about 30000 to about 200000, from about 30000 to about 100000, from about 40000 to about 500000, from about 40000 to about 400000, from about 40000 to about 300000, from about 40000 to about 200000, from about 40000 to about 100000, from about 50000 to about 500000, from about 50000 to about 400000, from about 50000 to about 300000, from about 50000 to about 200000, or from about 50000 to about 100000.

[0102] In some embodiments, the at least one terpenoid is released from the DES (for example at day 10) at a rate of less than about 1000 pg / cm2 / day, such as less than about 900, 800, 700, 600, 500, 450, 400, 350, 300, 250, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, less than about 10, or about 0 pg / cm2 / day, and useful ranges may be selected between any of these values (for example, from about 0 to about 1000, from about 0 to about 800, from about 0 to about 600, from about 0 to about 500, from about 0 to about 400, from about 0 to about 300, from about 0 to about 200, from about 0 to about 150, from about 0 to about 140, from about 0 to about 130, from about 0 to about 120, from about 0 to about 110, from about 0 to about 100, from about 0 to about 90, from about 0 to about 80, from about 0 to about 70, from about 0 to about 60, from about 0 to about 50, from about 20 to about 1000, from about 20 to about 800, from about 20 to about 600, from about 20 to about 500, from about 20 to about 400, from about 20 to about 300, from about 20 to about 200, from about 20 to about 150, from about 20 to about 140, from about 20 to about 130, from about 20 to about 120, from about 20 to about 110, from about 20 to about 100, from about 20 to about 90, from about 20 to about 80, from about 20 to about 70, from about 20 to about 60, from about 20 to about 50, from about 0 to about 1000, from about 30 to about 800, from about 30 to about 600, from about 30 to about 500, from about 30 to about 400, from about 30 to about 300, from about 30 to about 200, from about 30 to about 150, from about 30 to about 140, from about 30 to about 130, from about 30 to about 120, from about 30 to about 110, from about 30 to about 100, from about 30 to about 90, from about 30 to about 80, from about 30 to about 70, from about 30 to about 60, or from about 30 to about 50).

[0103] In some embodiments, the DES comprises at least two terpenoids, such as at least 3, 4, 5, 6, 7, 8, 9, or at least 10 terpenoids. In some embodiments, the DES comprises at least two terpenoic acids, such as at least 3, 4, 5, 6, 7, 8, 9, or at least 10 terpenoic acids.

[0104] In some embodiments, the DES is formed from the at least one terpenoid and a gymnosperm exudate comprising the at least one terpenoic acid. In some embodiments, the DES is formed from the at least one terpenoid and a conifer exudate comprising the at least one terpenoic acid. In some embodiments, the DES is formed from the at least one terpenoid and pine rosin comprising the at least one terpenoic acid. In some embodiments, the DES is formed from the at least one terpenoid and tall oil comprising the at least one terpenoic acid.

[0105] In some embodiments, the DES is formed from the at least one terpenoid and a gymnosperm exudate comprising at least two terpenoic acids. In some embodiments, the DES is formed from the at least one terpenoid and a conifer exudate comprising at least two terpenoic acids. In some embodiments, the DES is formed from the at least one terpenoid and pine rosin comprising at least two terpenoic acids. In some embodiments, the DES is formed from the at least one terpenoid and tall oil comprising at least two terpenoic acids.

[0106] In some embodiments, the DES is formed from a gymnosperm exudate (preferably pine rosin) and at least one terpenoid in a mass ratio of gymnosperm exudate:terpenoid of from about 1 :9 to about 9:1, for example from about 1:9 to about 9:1, from about 1 :9 to about 8:1, from about 1 :9 to about 7:1, from about 1:9 to about 6:1, from about 1 :9 to about 5:1, from about 1 :9 to about 4:1, from about 1 :9 to about 3:1, from about 1 :9 to about 2:1, from about 1:9 to about 1 :1, from about 1 :9 to about 1 :2, from about 1 :9 to about 1 :3, from about 1 :9 to about 1 :4, from about 1 :9 to about 1 :5, from about 1:9 to about 1 :6, from about 1:9 to about 1 :7, from about 1:9 to about 1 :8, from about 1 :5 to about 9:1, from about 1:5 to about 8:1, from about 1 :5 to about 7:1, from about 1 :5 to about 6:1, from about 1:5 to about 5:1, from about 1 :5 to about 4:1, from about 1 :5 to about 3:1, from about 1 :5 to about 2:1, from about 1 :5 to about 1 :1, from about 1:5 to about 1 :2, from about 1 :5 to about 1 :3, from about 1:5 to about 1 :4, from about 1 :3 to about 9:1, from about 1 :3 to about 8:1, from about 1:3 to about 7:1, from about 1:3 to about 6:1, from about 1:3 to about 5:1, from about 1 :3 to about 4:1, from about 1:3 to about 3:1, from about 1 :3 to about 2:1, from about 1 :3 to about 1 :1, from about 1:3 to about 1 :2, from about 1 :2 to about 9:1, from about 1 :2 to about 8:1, from about 1 :2 to about 7:1, from about 1 :2 to about 6:1, from about 1:2 to about 5:1, from about 1 :2 to about 4:1, from about 1 :2 to about 3:1, from about 1 :2 to about 2:1, from about 1 :2 to about 1 :1, from about 1:1 to about 9:1, from about 1:1 to about 8:1, from about 1:1 to about 7:1, from about 1 :1 to about 6:1, from about 1:1 to about 5:1, from about 1 :1 to about 4:1, from about 1 :1 to about 3:1, from about 1:1 to about 2:1). Preferably, the DES is formed from a gymnosperm exudate (preferably pine rosin) and at least one terpenoid in a mass ratio of gymnosperm exudate:terpenoid of from about 1 :1, about 3:2, about 7:3, about 4:9, or about 9:1.

[0107] In some embodiments, the at least one terpenoid comprises an alcohol group. In some embodiments, the at least one terpenoid comprises an aldehyde group. In some embodiments, the at least one terpenoid comprises a ketone group. In some embodiments, the at least one terpenoid comprises an alcohol, aldehyde, and / or ketone group.

[0108] In some embodiments, the at least one terpenoid comprises menthol, thymol, carvacrol, 4- carvomenthenol, camphor, eugenol, geraniol, trans trans-farnesol, 4-hexylresorcinol, cinnamyl alcohol, p-anisaldehyde, cuminaldehyde, (R)-(-)-carvone, (S)-(+)-carvone, citral, L-menthone, L- fenchone, trans-anethole, or any combination of any two or more of these.

[0109] In some embodiments, the at least one terpenoid comprises menthol, thymol, carvacrol, 4- carvomenthenol, camphor, eugenol, geraniol, trans trans-farnesol, 4-hexylresorcinol, cinnamyl alcohol, or any combination of any two or more of these. In some embodiments, the at least one terpenoid comprises p-anisaldehyde, cuminaldehyde, or both of these. In some embodiments, the at least one terpenoid comprises (R)-(-)-carvone, (S)-(+)-carvone, citral, L-menthone, L-fenchone, trans-anethole, or any combination of any two or more of these.

[0110] In some embodiments, the composition, the gymnosperm exudate, the rosin, or the at least one terpenoic acid comprises dehydroabietic acid, abietic acid, isopimeric acid, sandarapimeric acid, levopimeric acid, pimeric acid, or any combination of two or more of these. In some embodiments, the composition, the gymnosperm exudate, the rosin, or the at least one terpenoic acid comprises at least two of dehydroabietic acid, abietic acid, isopimeric acid, sandarapimeric acid, levopimeric acid, pimeric acid; preferably at least 3, 4, 5, or 6 of these. In some embodiments, the composition, the gymnosperm exudate, the rosin, or the at least one terpenoic acid comprises abietic acid and at least one additional terpenoic acid. In some embodiments, the composition, the gymnosperm exudate, the rosin, or the at least one terpenoic acid comprises abietic acid and at least one additional terpenoic acid selected from dehydroabietic acid, isopimeric acid, sandarapimeric acid, levopimeric acid, and pimeric acid. In some embodiments, the at least one additional terpenoic acid is present in the gymnosperm exudate or the rosin in an amount of at least about 0.1% w / w relative to the gymnosperm exudate or the rosin, such as at least about 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, or at least about 10.0% w / w, and useful ranges may be selected between any of these values (for example, from about 0.5% to about 10%, from about 0.5% to about 8%, from about 0.5% to about 6%, from about 1.5% to about 10%, from about 1.5% to about 8%, from about 1.5% to about 6%, from about 2.5% to about 10%, from about 2.5% to about 8%, or from about 2.5% to about 6%).

[0111] In some embodiments, the DES is formed from, or comprises, a source of terpenoic acid (preferably a gymnosperm exudate, more preferably a conifer exudate, most preferably pine rosin), wherein the source of terpenoic acid comprises at least about 20% w / w of one or more terpenoic acids, such as at least about 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or at least about 95% w / w, and useful ranges may be selected between any of these values (for example, from about 20% to about 95%, from about 20% to about 90%, from about 20% to about 85%, from about 20% to about 80%, from about 20% to about 75%, from about 20% to about 70%, from about 30% to about 95%, from about 30% to about 90%, from about 30% to about 85%, from about 30% to about 80%, from about 30% to about 75%, from about 30% to about 70%, from about 40% to about 95%, from about 40% to about 90%, from about 40% to about 85%, from about 40% to about 80%, from about 40% to about 75%, from about 40% to about 70%, from about 50% to about 95%, from about 50% to about 90%, from about 50% to about 85%, from about 50% to about 80%, from about 50% to about 75%, or from about 50% to about 70%).

[0112] In some embodiments, the glass transition temperature of the DES is at least about 4°C lower than the glass transition temperature of the abietic acid, gymnosperm exudate, or pine rosin from which the DES has been formed, such as at least about 6°C, 8°C, 10°C, 12°C, 14°C, 16°C, 18°C, 20°C, 22°C, 24°C, 26°C, 28°C, 30°C, 32°C, 34°C, 36°C, 38°C, 40°C, 42°C, 44°C, 46°C, 48°C, 50°C, 55°C, or at least about 60°C lower, and useful ranges may be selected between any of these values (for example, from about 4°C to about 60°C, from about 4°C to about 50°C, from about 4°C to about 44°C, from about 14°C to about 60°C, from about 14°C to about 50°C, from about 14°C to about 44°C, from about 24°C to about 60°C, from about 24°C to about 50°C, or from about 24°C to about 44°C lower). In some embodiments, the DES has a glass transition temperature of less than about 30°C, such as less than about 25°C, 20°C, 15°C, 10°C, 5°C, 0°C, -5°C, -10°C, -15°C, -20°C, -25°C, -30°C, -35°C, - 40°C, -45°C, -50°C, -55°C, or less than about -60°C, and useful ranges may be selected between any of these values (for example, from about -60°C to about 30°C, from about -60°C to about 10°C, from about -60°C to about 0°C, from about -60°C to about -10°C, from about -60°C to about - 20°C, from about -60°C to about -25°C, from about -60°C to about -30°C, from about -50°C to about 30°C, from about -50°C to about 10°C, from about -50°C to about 0°C, from about -50°C to about -10°C, from about -50°C to about -20°C, from about -50°C to about -25°C, from about -50°C to about -30°C, from about -45°C to about 30°C, from about -45°C to about 10°C, from about - 45°C to about 0°C, from about -45°C to about -10°C, from about -45°C to about -20°C, from about -45°C to about -25°C, or from about -45°C to about -30°C).

[0113] In some embodiments, the DES loses less than about 90% mass upon freeze drying for 48 hours, such as less than about 80%, 70%, 60%, 50%, 40%, 30%, 20%, 18%, 16%, 14%, 12%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.25%, 0.1%, or about 0%, and useful ranges may be selected between any of these values (for example, from about 0% to about 90%, from about 0% to about 70%, from about 0% to about 50%, from about 0% to about 30%, from about 0% to about 10%, from about 0% to about 5%, from about 0% to about 2%, from about 0% to about 1%, from about 0.1% to about 90%, from about 0.1% to about 70%, from about 0.1% to about 50%, from about 0.1% to about 30%, from about 0.1% to about 10%, from about 0.1% to about 5%, from about 0.1% to about 2%, from about 0.1% to about 1%, from about 2% to about 90%, from about 2% to about 70%, from about 2% to about 50%, from about 2% to about 30%, from about 2% to about 10%, from about 4% to about 90%, from about 4% to about 70%, from about 4% to about 50%, from about 4% to about 30%, or from about 4% to about 10%).

[0114] In some embodiments, the composition further comprises a buffering agent. In some embodiments, the DES and / or the composition has a pH that is lower than the pKa of the at least one terpenoic acid. In some embodiments, the pH of the DES and / or the composition is at least about 0.1 lower than the pKa of the at least one terpenoic acid, such as at least about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, or at least about 6.0 lower than the pKa of the at least one terpenoic acid, and useful ranges may be selected between any of these values (for example, from about 0.1 to about 6.0, from about 0.1 to about 5.0, from about 0.1 to about 4.0, from about 0.1 to about 3.0, from about 0.1 to about 2.0, from about 0.5 to about 6.0, from about 0.5 to about 5.0, from about 0.5 to about 4.0, from about 0.5 to about 3.0, from about 0.5 to about 2.0, from about 1.0 to about 6.0, from about 1.0 to about 5.0, from about 1.0 to about 4.0, from about 1.0 to about 3.0, or from about 1.0 to about 2.0).

[0115] In some embodiments, the DES and / or the composition has a pH of less than about 8.0, such as less than about 7.5, 7.0, 6.5, 6.0, 5.5, 5.0, 4.5, 4.0, 3.5, or less than about 3.0, and useful ranges may be selected between any of these values (for example, from about from about 3.0 to about 8.0, from about 3.0 to about 7.0, from about 3.0 to about 6.0, from about 3.0 to about 5.0, from about 3.0 to about 4.0, from about 4.0 to about 8.0, from about 4.0 to about 7.0, from about 4.0 to about 6.0, from about 4.0 to about 5.0, from about 5.0 to about 8.0, from about 5.0 to about 7.0, from about 5.0 to about 6.0, from about 6.0 to about 8.0, or from about 6.0 to about 7.0).

[0116] In some embodiments, the at least one terpenoid is non-ionic. In some embodiments, the at least one terpenoid is uncharged. In some embodiments, the at least one terpenoic acid is in its protonated form. In some embodiments, the at least one terpenoic acid is non-ionic. In some embodiments, the at least one terpenoic acid is uncharged. In some embodiments, at least about 50% by moles of the terpenoic acid relative to total terpenoic acids is non-ionic and / or protonated, such as at least about 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, or about 100%, and useful ranges may be selected between any of these values (for example, from about 50% to about 100%, from about 50% to about 98%, from about 50% to about 96%, from about 60% to about 100%, from about 60% to about 98%, from about 60% to about 96%, from about 70% to about 100%, from about 70% to about 98%, from about 70% to about 96%, from about 80% to about 100%, from about 80% to about 98%, from about 80% to about 96%, from about 90% to about 100%, from about 90% to about 98%, or from about 90% to about 96%).

[0117] In some embodiments, the at least one terpenoid and the at least one terpenoic acid form non- ionic interactions. In some embodiments, the at least one terpenoid and the at least one terpenoic acid form non-covalent interactions. In some embodiments, the at least one terpenoid and the at least one terpenoic acid form non-ionic, non-covalent interactions. In some embodiments, the interactions comprise one or more hydrogen bonds. In some embodiments, the one or more hydrogen bonds are formed between one or more carboxylic acid groups of the one or more terpenoic acids and one or more hydroxyl groups of the one or more terpenoids. In some embodiments, the DES does not comprise an ionic terpenoid. In some embodiments, the DES does not comprise an ionic terpenoic acid, and / or the at least one terpenoic acid is not in an ionic form. In some embodiments, the O-H stretching peak of a hydroxyl group of the one or more terpenoids forming part of the DES (for example, between about 3500-3000 cm'1, preferably at about 3177 and / or 3268 cm'1) is broadened and / or has reduced intensity compared to the O-H stretching group of the hydroxyl group of the one or more terpenoids when not forming a DES, as characterised by infrared spectroscopy; for example the peak intensity is reduced by at least about 10%, such as at least about 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or about 100%, and useful ranges may be selected between any of these values (for example, from about 10% to about 100%, from about 10% to about 80%, from about 10% to about 60%, from about 20% to about 100%, from about 20% to about 80%, or from about 20% to about 60%).

[0118] In some embodiments, the C=O stretching band of one or more terpenoic acids forming part of the DES is blue shifted compared to the C=O stretching band of the one or more terpenoic acids when not forming a DES, as characterised by infrared spectroscopy; for example blue shifted by at least about 0.5 cm'1, such as at least about 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or at least about 10 cm'1, and useful ranges may be selected between any of these values (for example, from about 0.5 to about 10, from about 0.5 to about 5, from about 1 to about 10, from about 1 to about 5).

[0119] In some embodiments, the functionalised or modified gymnosperm exudate comprises one or more properties that are modified compared to non-functionalised or unmodified gymnosperm exudate. In some embodiments, the one or more properties are selected from: a. viscosity, b. hydrophobicity, c. bioactivity, d. rate of release of the at least one terpenoid to air, e. rate of release of the at least one terpenoid to water, or f. any combination of any two or more of a to e.

[0120] In some embodiments, the arthropod control composition is a Varroa mite control composition. In some embodiments, the method of controlling arthropods is a method of controlling Varroa mites, preferably in a bee hive and / or apiary. In some embodiments, the treatment area is, or comprises, a bee hive and / or apiary.

[0121] In some embodiments, the pest control composition, arthropod control composition, or Varroa mite control composition comprises, consists essentially of, or consists of rosin and thymol. In some embodiments, the pest control composition, arthropod control composition, or Varroa mite control composition comprises a molar ratio of resin acids to thymol of about 6:1 to about 1 :6, such as about 5:1 to about 1:5, about 4:1 to about 1 :4, about 3:1 to about 1 :3, about 3:1 to about 1 :2, about 3:1 to about 1 :1, about 2:1 to about 1 :3, about 2:1 to about 1 :2, about 2:1 to about 1 :1, about 1 :1 to about 1 :3, about 1 :1 to about 1 :2, about 1.07:1, or about 1 :1.

[0122] In some embodiments, the pest control composition, arthropod control composition, or Varroa mite control composition is used in an amount of at least about 50 mg thymol per 1000 ml volume of the treatment area (for example, per 1000 ml volume of the bee hive and / or apiary), such as at least about 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, or at least about 1500 mg thymol, and useful ranges may be selected between any of these values (for example, from about 50 to about 1500, from about 50 to about 1000, from about 50 to about 750, from about 50 to about 500, from about 50 to about 400, from about 50 to about 300, from about 100 to about 1500, from about 100 to about 1000, from about 100 to about 750, from about 100 to about 500, from about 100 to about 400, from about 100 to about 300, from about 200 to about 1500, from about 200 to about 1000, from about 200 to about 750, from about 200 to about 500, from about 200 to about 400, from about 200 to about 300, from about 300 to about 1500, from about 300 to about 1000, from about 300 to about 750, from about 300 to about 500, from about 300 to about 400).

[0123] In some embodiments, exposure of Varroa destructor mites for 5 hours to air contacted with the DES, the pest control composition, or the arthropod control composition, at a concentration of 200 mg terpenoid per 1000 ml air, produces at least about X= 10% mortality of the mites, such as at least about 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or about 100%, and useful ranges may be selected between any of these values (for example, from about 10% to about 100%, from about 10% to about 80%, from about 10% to about 60%, from about 15% to about 100%, from about 15% to about 80%, from about 15% to about 60%, from about 20% to about 100%, from about 20% to about 80%, from about 20% to about 60%, from about 25% to about 100%, from about 25% to about 80%, from about 25% to about 60%, from about 30% to about 100%, from about 30% to about 80%, or from about 30% to about 60%).

[0124] In some embodiments, the DES, antimicrobial composition, antifungal composition, horticultural and / or viticultural composition, and / or plant wound healing composition is effective to reduce or prevent the growth of a plant pathogenic microorganism selected from the group consisting of Botryosphaeriaceae, Diatrypaceae, Aspergillaceae, Peronosporaceae, Nectriaceae, Venturiaceae, Colletotrichum gloeosporioides complex, Sclerotiniaceae, Taphrinaceae, Magnaporthaceae, Ceratobasidiaceae, Pleosporaceae, Burkholderiaceae, Rhizobiaceae; preferably Botryosphaeria sp., Eutypa lata, Ralstonia solanacearum, Candidatus Liberibacter spp, Penicillium digitatum, Lasiodiplodia theobromae, Phytophthora infestans, Fusarium oxysporum, Venturia inaequalis, Colletotrichum gloeosporioides, Botrytis cinerea, Taphrina spp., and Begomovirus.

[0125] In some embodiments, the DES releases the at least one terpenoid to air at a rate such that, after 1 week, the mass of the remaining terpenoid is at least about 25% w / w of that of the terpenoid originally present in the DES, such as at least about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.8%, 99.9%, or about 100%, and useful ranges may be selected between any of these values (for example, from about 25% to about 100%, from about 25% to about 90%, from about 25% to about 75%, from about 25% to about 50%, from about 50% to about 100%, from about 50% to about 75%, from about 75% to about 100%, from about 75% to about 95%, from about 75% to about 90%, from about 75% to about 85%, from about 75% to about 80%, from about 80% to about 100%, from about 80% to about 95%, from about 80% to about 90%, from about 80% to about 85%, from about 85% to about 100%, from about 85% to about 95%, from about 85% to about 90%, from about 90% to about 100%, from about 90% to about 95%, or from about 95% to about 100%).

[0126] In some embodiments, the DES releases the at least one terpenoid to air at a rate such that, after 2 weeks, the mass of the remaining terpenoid is at least about 25% w / w of that of the terpenoid originally present in the DES, such as at least about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.8%, 99.9%, or about 100%, and useful ranges may be selected between any of these values (for example, from about 25% to about 100%, from about 25% to about 90%, from about 25% to about 75%, from about 25% to about 50%, from about 50% to about 100%, from about 50% to about 75%, from about 75% to about 100%, from about 75% to about 95%, from about 75% to about 90%, from about 75% to about 85%, from about 75% to about 80%, from about 80% to about 100%, from about 80% to about 95%, from about 80% to about 90%, from about 80% to about 85%, from about 85% to about 100%, from about 85% to about 95%, from about 85% to about 90%, from about 90% to about 100%, from about 90% to about 95%, or from about 95% to about 100%).

[0127] In some embodiments, the DES releases the at least one terpenoid to air at a rate such that, after 9 weeks, the mass of the remaining terpenoid is at least about 25% w / w of that of the terpenoid originally present in the DES, such as at least about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.8%, 99.9%, or about 100%, and useful ranges may be selected between any of these values (for example, from about 25% to about 100%, from about 25% to about 90%, from about 25% to about 75%, from about 25% to about 50%, from about 50% to about 100%, from about 50% to about 75%, from about 75% to about 100%, from about 75% to about 95%, from about 75% to about 90%, from about 75% to about 85%, from about 75% to about 80%, from about 80% to about 100%, from about 80% to about 95%, from about 80% to about 90%, from about 80% to about 85%, from about 85% to about 100%, from about 85% to about 95%, from about 85% to about 90%, from about 90% to about 100%, from about 90% to about 95%, or from about 95% to about 100%).

[0128] In some embodiments, the DES releases the at least one terpenoid at a first rate over a first time period, and at a second rate over a second time period subsequent to the first time period, wherein the first rate is higher than the second rate. In some embodiments, the first time period is from about day 0 to about day 21 of exposing the DES to air or water, or from about day 0 to about day 14, or from about day 0 to about day 7. In some embodiments, the second time period is from about day 21 of exposing the DES to air or water onwards, or from about day 14 onwards, or about day 7 onwards. In some embodiments, the second time period is from about day 21 to about day 42 of exposing the DES to air or water, or from about day 14 to about day 42, or from about day 7 to about day 42.

[0129] In some embodiments, the DES, or the biofouling control composition, releases the at least one terpenoid to water at a rate such that, after 7 days, the mass of the remaining terpenoid is at least about 20% w / w of that of the terpenoid originally present in the DES, such as at least about 30%, 40%, 50%, 60%, 70%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.8%, 99.9%, or about 100%, and useful ranges may be selected between any of these values (for example, from about 20% to about 100%, from about 20% to about 95%, from about 20% to about 90%, from about 40% to about 100%, from about

[0130] 40% to about 95%, from about 40% to about 90%, from about 60% to about 100%, from about

[0131] 60% to about 95%, from about 60% to about 90%, from about 80% to about 100%, from about

[0132] 80% to about 95%, from about 80% to about 90%, from about 90% to about 100%, from about

[0133] 90% to about 99%, from about 90% to about 98%, from about 92% to about 100%, from about

[0134] 92% to about 99%, from about 92% to about 98%, from about 94% to about 100%, from about

[0135] 94% to about 99%, from about 94% to about 98%, from about 96% to about 100%, from about

[0136] 96% to about 99%, from about 96% to about 98%, from about 98% to about 100%, or from about 98% to about 99%).

[0137] In some embodiments, the DES, or the biofouling control composition, releases the at least one terpenoid to water at a rate such that, after 14 days, the mass of the remaining terpenoid is at least about 20% w / w of that of the terpenoid originally present in the DES, such as at least about 30%, 40%, 50%, 60%, 70%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.8%, 99.9%, or about 100%, and useful ranges may be selected between any of these values (for example, from about 20% to about 100%, from about 20% to about 95%, from about 20% to about 90%, from about 40% to about 100%, from about

[0138] 40% to about 95%, from about 40% to about 90%, from about 60% to about 100%, from about

[0139] 60% to about 95%, from about 60% to about 90%, from about 80% to about 100%, from about

[0140] 80% to about 95%, from about 80% to about 90%, from about 90% to about 100%, from about

[0141] 90% to about 99%, from about 90% to about 98%, from about 92% to about 100%, from about

[0142] 92% to about 99%, from about 92% to about 98%, from about 94% to about 100%, from about

[0143] 94% to about 99%, from about 94% to about 98%, from about 96% to about 100%, from about

[0144] 96% to about 99%, from about 96% to about 98%, from about 98% to about 100%, or from about 98% to about 99%).

[0145] In some embodiments, the DES, or the biofouling control composition, has an EC50 against T. maritimum of less than about 50 pg / mL, such as less than about 40, 30, 25, 25, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, or less than about 1 pg / mL, and useful ranges may be selected between any of these values (for example, from about 1 to about 40, from about 1 to about 30, from about 1 to about 20, from about 1 to about 15, from about 1 to about 10, from about 1 to about 5, from about 2 to about 40, from about 2 to about 30, from about 2 to about 20, from about 2 to about 15, from about 2 to about 10, from about 3 to about 40, from about 3 to about 30, or from about 3 to about 20).

[0146] In some embodiments, the DES, or the biofouling control composition, has an EC50 against C. closterium of less than about 200 pg / mL, such as less than about 150, 100, 75, 50, 40, 30, 20, 10, 8, 6, 4, 2, or less than about 1 pg / mL, and useful ranges may be selected between any of these values (for example, from about 1 to about 200, from about 1 to about 100, from about 1 to about 50, from about 1 to about 30, from about 1 to about 20, from about 1 to about 15, from about 1 to about 10, from about 3 to about 200, from about 3 to about 100, from about 3 to about 50, from about 3 to about 30, from about 3 to about 20, from about 3 to about 15, from about 3 to about 10, from about 5 to about 200, from about 5 to about 100, from about 5 to about 50, from about 5 to about 30, from about 5 to about 20, from about 5 to about 15, or from about 5 to about 10).

[0147] In some embodiments, the DES, or the biofouling control composition, has an EC50 against C. savignyi of less than about 10 pg / mL, such as less than about 9, 8, 7, 6, 5, 4, 3, 2, or less than about 1 pg / mL, and useful ranges may be selected between any of these values (for example, from about 1 to about 10, from about 1 to about 5, or from about 1 to about 2).

[0148] In some embodiments, the DES, or the biofouling control composition, has an EC50 against M. edulis of less than about 20 pg / mL, such as less than about 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, or less than about 1 pg / mL, and useful ranges may be selected between any of these values (for example, from about 1 to about 20 from about 1 to about 10, from about 1 to about 5, from about 1 to about 3, from about 2 to about 20, from about 2 to about 10, or from about 2 to about 5).

[0149] In some embodiments, the DES, or the biofouling control composition has an EC50 against two or more of T. maritimum, C. Closterium, C. savignyi, and M. edulis of less than about 200 pg / mL, such as less than about 150, 100, 75, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, or less than about 1 pg / mL, and useful ranges may be selected between any of these values (for example, from about 1 to about 200, from about 1 to about 100, from about 1 to about 50, from about 1 to about 30, from about 1 to about 20, from about 1 to about 15, from about 1 to about 10, from about 3 to about 200, from about 3 to about 100, from about 3 to about 50, from about 3 to about 30, from about 3 to about 20, from about 3 to about 15, from about 3 to about 10, from about 5 to about 200, from about 5 to about 100, from about 5 to about 50, from about 5 to about 30, from about 5 to about 20, from about 5 to about 15, or from about 5 to about 10); preferably against three or more of T. maritimum, C. Closterium, C. savignyi, and M. edulis; more preferably against all four of these. In some embodiments, the DES or the antimicrobial composition has antimicrobial activity against one or more bacteria, fungi, and / or viruses. In some embodiments, the DES or the antimicrobial composition has antimicrobial activity against one or more bacteria. In some embodiments, the DES or the antimicrobial composition has antimicrobial activity against one or more fungi. In some embodiments, the DES or the antimicrobial composition has antimicrobial activity against one or more viruses. In some embodiments, the DES or the antimicrobial composition has antimicrobial activity against one or more pathogenic microorganisms. In some embodiments, the DES or the antimicrobial composition has antimicrobial activity against one or more bacterial pathogens.

[0150] In some embodiments, the one or more bacteria (for example, the one or more bacterial pathogens) comprise one or more species of Vibrio and / or Listeria, preferably Vibrio parahaemolyticus and / or Listeria monocytogenes. In some embodiments, the DES or the antimicrobial composition has antimicrobial activity against one or more biofilm-forming microbes (for example, one or more biofilm-forming bacteria). In some embodiments, the DES or the antimicrobial composition has antimicrobial activity against one or more food-borne human pathogens.

[0151] In some embodiments, the DES or the composition has antimicrobial activity against one or more microbes that cause infections, diseases, and / or disorders of hoof and / or horn. In some embodiments, the composition is a hoof protecting composition. In some embodiments, the composition is a horn protecting composition. In some embodiments, the composition is a hoof and / or horn protecting composition.

[0152] In some embodiments, the DES or the antimicrobial composition is effective against pathogens of apiculture, for example European foulbrood and / or American foulbrood bacteria. In some embodiments, the DES or the antimicrobial composition is effective against bacteria from the Enterococcaceae and / or Paenibacillaceae families, preferably against bacteria from the Melissococcus and / or Paenibacillus genuses, more preferably against Melissococcus plutonius and / or Paenibacillus spp. bacteria. In some embodiments, the composition is a composition for use in apiculture. In some embodiments, the treatment area is, or comprises, a bee hive and / or apiary.

[0153] In some embodiments, the DES or the antimicrobial composition has an antimicrobial activity such that, when an amount of the DES or the composition sufficient to provide 5 mg of the at least one terpenoid is applied to the centre of an agar plate inoculated with Listeria monocytogenes and / or Vibrio parahaemolyticus, a growth inhibition zone forms after 48 hours that has a radius of at least about 5 mm, such as at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or at least about 60 mm in diameter, and useful ranges may be selected between any of these values (for example, from about 5 to about 60, from about 5 to about 50, from about 5 to about 40, from about 5 to about 30, from about 10 to about 60, from about 10 to about 50, from about 10 to about 40, from about 10 to about 30, from about 15 to about 60, from about 15 to about 50, from about 15 to about 40, from about 15 to about 30, from about 20 to about 60, from about 20 to about 50, from about 20 to about 40, from about 20 to about 30, from about 25 to about 60, from about 25 to about 50, from about 25 to about 40, from about 25 to about 30, from about 30 to about 60, from about 30 to about 50, from about 30 to about 40).

[0154] In some embodiments, the DES or the antimicrobial composition has an antimicrobial activity such that, when about 10 mg of the DES or the composition is contacted with 2.5 ml of bacteria- containing liquid (preferably wherein the bacteria are Listeria monocytogenes and / or Vibrio parahaemolyticus), the amount of live bacteria in the liquid is reduced by at least about 50% after 3 days, such as at least about 60%, 70%, 80%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, 99.99%, or about 100%, and useful ranges may be selected between any of these values (for example, from about 50% to about 100%, from about 50% to about 99.5%, from about 50% to about 99%, from about 60% to about 100%, from about 60% to about 99.5%, from about 60% to about 99%, from about 70% to about 100%, from about 70% to about 99.5%, from about 70% to about 99%, from about 80% to about 100%, from about 80% to about 99.5%, from about 80% to about 99%, from about 90% to about 100%, from about 90% to about 99.5%, from about 90% to about 99%, from about 95% to about 100%, from about 99% to about 100%, or from about 99.5% to about 100%).

[0155] In some embodiments, the DES or the antimicrobial composition has an antimicrobial activity such that, when about 20 mg of the DES or the composition is contacted with 2.5 ml of bacteria- containing liquid (preferably wherein the bacteria are Listeria monocytogenes and / or Vibrio parahaemolyticus), the amount of live bacteria in the liquid is reduced by at least about 50% after 3 days, such as at least about 60%, 70%, 80%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, 99.99%, or about 100%, and useful ranges may be selected between any of these values (for example, from about 50% to about 100%, from about 50% to about 99.5%, from about 50% to about 99%, from about 60% to about 100%, from about 60% to about 99.5%, from about 60% to about 99%, from about 70% to about 100%, from about 70% to about 99.5%, from about 70% to about 99%, from about 80% to about 100%, from about 80% to about 99.5%, from about 80% to about 99%, from about 90% to about 100%, from about 90% to about 99.5%, from about 90% to about 99%, from about 95% to about 100%, from about 99% to about 100%, or from about 99.5% to about 100%).

[0156] It is intended that reference to a range of numbers disclosed herein (for example, 1 to 10) also incorporates reference to all rational numbers within that range (for example, 1, 1.1, 2, 3, 3.9, 4, 5, 6, 6.5, 7, 8, 9 and 10) and also any range of rational numbers within that range (for example, 2 to 8, 1.5 to 5.5 and 3.1 to 4.7) and, therefore, all sub-ranges of all ranges expressly disclosed herein are hereby expressly disclosed. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner.

[0157] This invention may also be said broadly to consist in the parts, elements and features referred to or indicated in the specification of the application, individually or collectively, and any or all combinations of any two or more said parts, elements or features, and where specific integers are mentioned herein which have known equivalents in the art to which this invention relates, such known equivalents are deemed to be incorporated herein as if individually set forth.

[0158] Although the present invention is broadly as defined above, those persons skilled in the art will appreciate that the invention is not limited thereto and that the invention also includes embodiments of which the following description gives examples.

[0159] In the description in this specification reference may be made to subject matter which is not within the scope of the claims of the current application. That subject matter should be readily identifiable by a person skilled in the art and may assist in putting into practice the invention as defined in the claims of this application.

[0160] Detailed description of the invention

[0161] The inventors have surprisingly found that natural deep eutectic systems (NaDES) formed from mixtures of primary and / or secondary plant metabolites have a variety of useful properties, including biofouling control properties.

[0162] Accordingly, in a first aspect the invention provides a deep eutectic system (DES) formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoic acid is present in a gymnosperm exudate. Definitions

[0163] Unless otherwise stated, the singular forms "a", "an" and "the" include the plural reference.

[0164] The term "(s)" following a noun as used herein means the plural and / or singular form of that noun.

[0165] The term "about" as used herein generally refers to a range of numerical values (e.g. ± 5 to 10% of the recited value) that those skilled in the art would consider equivalent to the recited value. Ranges can be expressed herein as from "about" one particular value, and / or to "about" another particular value. When such a range is expressed, the range is inclusive of the recited values.

[0166] The term "and / or" as used herein means "and" or "or", or both.

[0167] The term "biofouling" as used herein means the accumulation of biological organisms on surfaces. Biofouling may be caused by microorganisms, plants, algae, cnidaria, arthropods, molluscs, tunicate, and / or sponges. Biofouling can occur in almost all circumstances where materials have interfaces with air or water, and is a particular problem for materials in marine environments. Biofouling may also pose a problem in industrial (e.g. food processing), medical (e.g. hospitals, clinics), commercial, and other terrestrial settings.

[0168] The term "biofouling control composition" as used herein means any composition useful for reducing or preventing biofouling, affecting succession of biofouling organisms, or selectively encouraging the growth of preferential fouling organisms. Biofouling control compositions that reduce or prevent biofouling are also known as antifouling compositions. Some biofouling control compositions reduce or prevent the ability of biofouling organisms to adhere to a surface, for example by presenting a non-stick coating. These coatings may also reduce the strength of adherence, allowing any biofouling organisms that do adhere to be easily removed. Other biofouling control compositions prevent growth by producing high concentrations of biocide at a coating surface, contain peroxides (or peroxide producing systems), or continuously shed to prevent organism adhesion.

[0169] The term "comprising" as used herein means "consisting at least in part of". When interpreting statements in this specification and claims which include the term "comprising", other features besides the features prefaced by this term in each statement can also be present. Related terms such as "comprise" and "comprised" are to be interpreted in similar manner. The term "control" and "controlling" (and similar grammatical constructions) as used herein with regards to arthropods such as insects and / or arachnids, or with regards to plant pests, means that the compositions and / or methods are effective to repel, deter, inhibit the growth and / or survival of, increase the morbidity of, and / or kill, arthropods or plant pests. In some embodiments, controlling comprises deterring or repelling the targeted organisms from an area, such as a surface to which the composition has been applied, or a space adjacent to such a surface. In some embodiments, controlling comprises killing the targeted organisms, for example killing them when they come into contact with a surface to which the composition has been applied, or when they are present in a space adjacent to such a surface.

[0170] The terms "deep eutectic system" or "DES" as used herein means a mixture of components that has a lower melting point than individual elements of the mixture; for example, a DES may be liquid at room temperature, while the individual components are solid at room temperature. DES often comprise a combination of a Lewis or Bronsted acid and a base.

[0171] The terms "natural deep eutectic system" or "NaDES" as used herein means a DES that is formed primarily from naturally occurring components, such as plant primary and / or secondary metabolites.

[0172] The term "fragrance-releasing composition" as used herein means a composition that comprises, and is capable of releasing, one or more scent compounds.

[0173] The term "gymnosperm exudate" as used herein means a substance such as a sap, resin, gum, or pitch exuded by a gymnosperm plant, often in response to wounding. Gymnosperm exudate is often a highly viscous liquid, and may solidify. One exemplary embodiment of a gymnosperm exudate is pine resin.

[0174] The terms "ionic" and "non-ionic" as used herein in relation to terpenoids and / or terpenoic acids refers to whether the terpenoid / terpenoic acid carries a net electrical charge in the DES. For example, menthol and thymol do not carry a net electrical charge, and would therefore be considered non-ionic. It will be appreciated that certain compounds, in particular weak acids, may be protonated or deprotonated (i.e. charged or uncharged, and ionic or non-ionic) depending on pH. For example, abietic acid may be protonated (and therefore non-ionic) at low pH, but deprotonated (and therefore ionic) at higher pH. The term "plant" as used herein encompasses whole plants and all parts of a plant from all stages of a plant lifecycle including but not limited to vegetative and reproductive cells and tissues, propagules, seeds, embryos, fruits, shoots, stems, leaves, leaf sheaths and blades, inflorescences, roots, anthers, ligules, palisade, mesophyll, epidermis, auricles, palea, lemma and tillers.

[0175] The term "resin acid" as used herein means a carboxylic acid found in gymnosperm exudates. Most resin acids have a structure comprising three fused rings with the empirical formula C19H29COOH. Resin acids may be terpenoic acids, such as diterpenoic acids. One exemplary embodiment of a resin acid is abietic acid.

[0176] The term "rosin" as used herein means a solid form of resin obtained from trees, in particular gymnosperms such as conifers. Rosin may be prepared by evaporation of volatile resin components. The major component of rosin typically comprises various resin acids such as abietic acid.

[0177] The term "scent compound" as used herein means a volatile compound that can be perceived via the sense of smell, i.e. that has an odour. Preferably, the scent compound has a pleasant odour. Exemplary embodiments of scent compounds include various monoterpenes, sesquiterpenes, or monoterpenoids such as linalool, cineol, citral, eucalyptol, geraniol, limonene, menthol, phenylethanol, pinene, terpineol and thymol; or sesquiterpenoids such as cadinene, calamine, bulgarene, cubeol, cadinol, and farnesol.

[0178] The term "tall oil" as used herein means the liquid obtained as a by-product of the Kraft process of wood pulp manufacture when pulping coniferous trees. While the composition of tall oil varies depending on the type of wood used, it typically contains rosins (including resin acids such as abietic acid and its isomers) as well as fatty acids, fatty alcohols, and sterols.

[0179] The term "terpene" as used herein refers to a class of plant secondary metabolites derived from two or more isoprene units. Terpenes have the formula (CsHs)n for n > 2. The term "terpenoid" as used herein refers a terpene that has been functionalised, modified, substituted, or derivatised. This may include the addition of one or more oxygen atoms and / or the movement or removal of one or more methyl groups.

[0180] Terpenes and terpenoids may be classified according to the number of isoprene units that make up the parent terpene. Hemiterpenoids are terpenoids derived from one isoprene unit; monoterpenoids from two; sesquiterpenoids from three; and diterpenoids from four isoprene units. Exemplary embodiments of monoterpenoids include menthol and thymol, and one exemplary embodiment of a diterpenoid is abietic acid.

[0181] The term "terpenoic acid" as used herein means a terpenoid comprising one or more carboxylic acid groups. Similarly, the term "diterpenoic acid" as used herein means a diterpenoid comprising one or more carboxylic acid groups. One exemplary embodiment of a diterpenoic acid is abietic acid.

[0182] The term "oxygenated terpenoid" as used herein means a terpenoid comprising one or more oxygen atoms. The term "hydroxylated terpenoid" as used herein means a terpenoid comprising one or more hydroxyl groups. Similarly, the term "monohydroxylated terpenoid" as used herein means a terpenoid comprising one hydroxyl group. Exemplary embodiments of monohydroxylated terpenoids include menthol and thymol.

[0183] Deep eutectic systems

[0184] Deep eutectic systems (DES) are mixtures of components wherein the mixture has a lower melting point than the individual elements of the mixture. In some embodiments, a DES may also have a lower viscosity than the individual elements of the DES.

[0185] In some embodiments, the melting point of the DES is at least about 1 °C lower than the melting point of one or more components of the DES (preferably at least about 1°C lower than each component of the DES), such as at least about 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 12°C, 14°C, 16°C, 18°C, 20°C, 22°C, 24°C, 26°C, 28°C, 30°C, 35°C, 40°C, 45°C, or at least about 50°C lower than the melting point of one or more components of the DES (preferably than each component of the DES).

[0186] In some embodiments, the DES has a melting point of less than about 60°C, such as less than about 58°C, less than about 56°C, less than about 55°C, less than about 54°C, less than about 52°C, less than about 50°C, less than about 48°C, less than about 46°C, less than about 45°C, less than about 44°C, less than about 42°C, less than about 40°C, less than about 38°C, less than about 36°C, less than about 35°C, less than about 34°C, less than about 32°C, less than about 30°C, less than about 28°C, less than about 26°C, less than about 25°C, less than about 24°C, less than about 22°C, less than about 20°C, less than about 18°C, less than about 16°C, less than about 15°C, less than about 14°C, less than about 12°C, less than about 10°C, less than about 8°C, less than about 6°C, less than about 5°C, less than about 4°C, less than about 2°C, less than about 0°C, less than about - 10°C, less than about -20°C, less than about -30°C, less than about -40°C, less than about -50°C, less than about -60°C, less than about -70°C, less than about -80°C, less than about -90°C, or less than about -100°C, and useful ranges may be selected between any of these value (for example, from about -100°C to about 60°C, from about -100°C to about 55°C, from about -100°C to about 50°C, from about -100°C to about 45°C, from about -100°C to about 40°C, from about -100°C to about 35°C, from about -100°C to about 30°C, from about -100°C to about 25°C, from about -50°C to about 60°C, from about -50°C to about 55°C, from about -50°C to about 50°C, from about -50°C to about 45°C, from about -50°C to about 40°C, from about -50°C to about 35°C, from about -50°C to about 30°C, from about -50°C to about 25°C, from about -20°C to about 60°C, from about -20°C to about 55°C, from about -20°C to about 50°C, from about -20°C to about 45°C, from about -20°C to about 40°C, from about -20°C to about 35°C, from about -20°C to about 30°C, from about -20°C to about 25°C, from about 0°C to about 60°C, from about 0°C to about 55°C, from about 0°C to about 50°C, from about 0°C to about 45°C, from about 0°C to about 40°C, from about 0°C to about 35°C, from about 0°C to about 30°C, from about 0°C to about 25°C, from about 5°C to about 60°C, from about 5°C to about 55°C, from about 5°C to about 50°C, from about 5°C to about 45°C, from about 5°C to about 40°C, from about 5°C to about 35°C, from about 5°C to about 30°C, from about 5°C to about 25°C, from about 10°C to about 60°C, from about 10°C to about 55°C, from about 10°C to about 50°C, from about 10°C to about 45°C, from about 10°C to about 40°C, from about

[0187] 10°C to about 35°C, from about 10°C to about 30°C, from about 10°C to about 25°C, from about

[0188] 15°C to about 60°C, from about 15°C to about 55°C, from about 15°C to about 50°C, from about

[0189] 15°C to about 45°C, from about 15°C to about 40°C, from about 15°C to about 35°C, from about

[0190] 15°C to about 30°C, from about 15°C to about 25°C, from about 20°C to about 60°C, from about

[0191] 20°C to about 55°C, from about 20°C to about 50°C, from about 20°C to about 45°C, from about

[0192] 20°C to about 40°C, from about 20°C to about 35°C, from about 20°C to about 30°C, or from about 20°C to about 25°C).

[0193] DES often comprise a combination of one or more hydrogen bond donors and one or more hydrogen bond acceptors. In some embodiments, the DES comprises, consists essentially of, or consists of one or more hydrogen bond donors and one or more hydrogen bond acceptors. In some embodiments, the DES comprises, consists essentially of, or consists of one or more terpenoic acids and one or more terpenoids, preferably one or more oxygenated terpenoids.

[0194] Without wishing to be bound by theory, it is believed that the one or more carboxylic acid groups of the one or more terpenoic acids are able to form hydrogen bond(s) with the one or more oxygen groups of the one or more terpenoids, thereby forming a DES interaction. For example, without wishing to be bound by theory, it is believed that the carboxylic acid group of abietic acid is able to form a hydrogen bond with the hydroxyl group of menthol or thymol, thereby allowing the combination of abietic acid + menthol, or abietic acid + thymol, to form a DES.

[0195] The ratio of the components of the DES may be varied to adjust the properties of the DES. For example, in some embodiments the viscosity of the DES may be selected by selecting an appropriate ratio of components as needed. Without wishing to be bound by theory, it is believed that the molar ratio of hydrogen bond donors (or hydrogen bond donating groups) to hydrogen bond acceptors (or hydrogen bond accepting groups) may be varied to adjust the properties of the DES. It will be appreciated that some hydrogen bond donors (such as terpenoic acids) may comprise more than one hydrogen bond donating group (such as more than one carboxylic acid group). Similarly, some hydrogen bond acceptors (such as terpenoids) may comprise more than one hydrogen bond accepting group (such as more than one hydroxyl group). In such cases, the ratio of hydrogen bond donors to hydrogen bond acceptors may not be the same as the ratio of hydrogen bond donating groups to hydrogen bond accepting groups.

[0196] In some embodiments, the molar ratio of hydrogen bond donating groups to hydrogen bond accepting groups, or the molar ratio of hydrogen bond donors to hydrogen bond acceptors, or the ratio of terpenoic acids to terpenoids, is from about 6:1 to about 1:6, such as from about 6:1 to about 1:5, from about 6:1 to about 1:4, from about 6:1 to about 1:3, from about 6:1 to about 1:2, from about 6:1 to about 1:1, from about 5:1 to about 1:6, from about 5:1 to about 1:5, from about 5:1 to about 1:4, from about 5:1 to about 1:3, from about 5:1 to about 1:2, from about 5:1 to about 1:1, from about 4:1 to about 1:6, such as from about 4:1 to about 1:5, from about 4:1 to about 1:4, from about 4:1 to about 1:3, from about 4:1 to about 1:2, from about 4:1 to about 1:1, from about 3:1 to about 1:6, such as from about 3:1 to about 1:5, from about 3:1 to about 1:4, from about 3:1 to about 1:3, from about 3:1 to about 1:2, from about 3:1 to about 1:1, from about 2:1 to about 1:6, such as from about 2:1 to about 1:5, from about 2:1 to about 1:4, from about 2:1 to about 1:3, from about 2:1 to about 1:2, from about 2:1 to about 1:1, from about 1:1 to about 1:6, such as from about 1:1 to about 1:5, from about 1:1 to about 1:4, from about 1:1 to about 1:3, from about 1:1 to about 1:2, or about 1:1. Viscosity of a DES may be measured using means known in the art e.g. viscometry and / or rheometry. The viscosity of the DES may be selected based on the desired application, for example by selecting the components of the DES or their molar ratio.

[0197] In some embodiments, the viscosity of the DES is from about 100 mPa-s to about 1,000,000 mPa-s for Newtonian fluids within the temperature range of -10 to 60°C, preferably at 20°C. Preferably, the viscosity of the DES is from about 100 to about 1,000,000 mPa-s at a temperature of about 20°C, such as from about 500 to about 1000000, from about 500 to about 750000, from about 500 to about 500000, from about 500 to about 100000, from about 500 to about 50000, from about 1000 to about 1000000, from about 1000 to about 750000, from about 1000 to about 500000, from about 1000 to about 100000, from about 1000 to about 50000, from about 5000 to about 1000000, from about 5000 to about 750000, from about 5000 to about 500000, from about 5000 to about 100000 from about 5000 to about 50000, from about 10000 to about 1000000, from about 10000 to about 750000, from about 10000 to about 500000, from about 10000 to about 100000, from about 10000 to about 50000, from about 20000 to about 1000000, from about 20000 to about 750000, from about 20000 to about 500000, from about 20000 to about 100000, from about 20000 to about 50000, from about 30000 to about 1000000, from about 30000 to about 750000, from about 30000 to about 500000, from about 30000 to about 100000, from about 30000 to about 50000, from about 40000 to about 1000000, from about 40000 to about 750000, from about 40000 to about 500000, from about 40000 to about 100000, from about 40000 to about 50000, from about 50000 to about 1000000, from about 50000 to about 750000, from about 50000 to about 500000, or from about 50000 to about 100000 mPa-s.

[0198] In some embodiments, the viscosity of the DES is from about 1 mPa-s to about 500,000 mPa-s for non-Newtonian fluids within the temperature range of -10 to 60°C (preferably at 20°C), over the shear rate of 0.1 to 10,000 s’1, such as from about 100 to about 500000, from about 100 to about 400000, from about 100 to about 300000, from about 100 to about 200000, from about 100 to about 100000, from about 1000 to about 500000, from about 1000 to about 400000, from about 1000 to about 300000, from about 1000 to about 200000, from about 1000 to about 100000, from about 10000 to about 500000, from about 10000 to about 400000, from about 10000 to about 300000, from about 10000 to about 200000, from about 10000 to about 100000, from about 20000 to about 500000, from about 20000 to about 400000, from about 20000 to about 300000, from about 20000 to about 200000, from about 20000 to about 100000, from about 30000 to about 500000, from about 30000 to about 400000, from about 30000 to about 300000, from about 30000 to about 200000, from about 30000 to about 100000, from about 40000 to about 500000, from about 40000 to about 400000, from about 40000 to about 300000, from about 40000 to about 200000, from about 40000 to about 100000, from about 50000 to about 500000, from about 50000 to about 400000, from about 50000 to about 300000, from about 50000 to about 200000, or from about 50000 to about 100000.

[0199] In some embodiments, the viscosity is measured at a shear rate of about 0.1 s’1, or about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 5.0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, or about 10000 s’1. In some embodiments, the viscosity is at a temperature of about -10°C, or about -5, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or about 60°C.

[0200] A DES may have a reduced release rate of its components in air compared to the release rate of the individual components when not in a DES. Release rate may be determined by any suitable method, for example by measuring the mass loss after exposing to air for a time period.

[0201] A DES may also have a reduced release rate of its components upon freeze-drying compared to the individual components when not in a DES. In some embodiments, the DES loses less than about 50% of its weight upon freeze drying, such as less than about 40%, less than about 30%, less than about 20%, less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, less than about 0.9%, less than about 0.8%, less than about 0.7%, less than about 0.6%, less than about 0.5%, less than about 0.4%, less than about 0.3%, less than about 0.2%, less than about 0.1%, or about 0%, and useful ranges may be selected between any of these values (for example, from about 0% to about 50%, from about 0% to about 40%, from about 0% to about 30%, from about 0% to about 20%, from about 0% to about 10%, from about 0% to about 9%, from about 0% to about 8%, from about 0% to about 7%, from about 0% to about 6%, from about 0% to about 5%, from about 0% to about 4%, from about 0% to about 3%, from about 0% to about 2%, from about 0% to about 1%, from about 0% to about 0.9%, or from about 0% to about 0.8%).

[0202] A DES may have a reduced release rate of its components in water compared to the release rate of the individual components when not in a DES. Release rate may be determined by any suitable method. One method is described in Example 2. It will be appreciated that the release rate may vary over time. For example, a DES may have an initially high release rate when placed in contact with water, but that release rate may reduce to an approximately steady-state level after several days (such as by day 11).

[0203] In some embodiments, the at least one terpenoid and / or the at least one terpenoic acid is released from the DES (for example, after immersion in water for 11 days, or after exposure to air for 11 days) at a rate of less than about 1000 pg / cm2 / day, such as less than about 900, 800, 700, 600, 500, 450, 400, 350, 300, 250, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, less than about 10, or about 0 pg / cm2 / day, and useful ranges may be selected between any of these values (for example, from about 0 to about 1000, from about 0 to about 800, from about 0 to about 600, from about 0 to about 500, from about 0 to about 400, from about 0 to about 300, from about 0 to about 200, from about 0 to about 150, from about 0 to about 140, from about 0 to about 130, from about 0 to about 120, from about 0 to about 110, from about 0 to about 100, from about 0 to about 90, from about 0 to about 80, from about 0 to about 70, from about 0 to about 60, from about 0 to about 50, from about 20 to about 1000, from about 20 to about 800, from about 20 to about 600, from about 20 to about 500, from about 20 to about 400, from about 20 to about 300, from about 20 to about 200, from about 20 to about 150, from about 20 to about 140, from about 20 to about 130, from about 20 to about 120, from about 20 to about 110, from about 20 to about 100, from about 20 to about 90, from about 20 to about 80, from about 20 to about 70, from about 20 to about 60, from about 20 to about 50, from about 0 to about 1000, from about 30 to about 800, from about 30 to about 600, from about 30 to about 500, from about 30 to about 400, from about 30 to about 300, from about 30 to about 200, from about 30 to about 150, from about 30 to about 140, from about 30 to about 130, from about 30 to about 120, from about 30 to about 110, from about 30 to about 100, from about 30 to about 90, from about 30 to about 80, from about 30 to about 70, from about 30 to about 60, or from about 30 to about 50).

[0204] A DES may lose less mass when in contact with water than the individual components when not in a DES. Mass loss may be determined by measuring the initial mass of DES coating a surface, contacting with water for a period of time (such as 15 days), and measuring the final mass of the DES. In some embodiments, the DES loses less than about 60% (w / w) of its mass when in contact with water for 15 days, such as less than about 55%, less than about 50%, less than about 45%, less than about 40%, less than about 35%, less than about 30%, less than about 25%, less than about 20%, less than about 15%, less than about 10%, less than about 5%, or about 0%, and useful ranges may be selected between any of these values (for example, from about 0% to about 60%, from about 0% to about 55%, from about 0% to about 50%, from about 0% to about 45%, from about 0% to about 40%, from about 0% to about 35%, from about 0% to about 30%, from about 0% to about 25%, from about 0% to about 20%, from about 0% to about 15%, from about 5% to about 60%, from about 5% to about 55%, from about 5% to about 50%, from about 5% to about 45%, from about 5% to about 40%, from about 5% to about 35%, from about 5% to about 30%, from about 5% to about 25%, from about 5% to about 20%, from about 5% to about 15%, from about 10% to about 60%, from about 10% to about 55%, from about 10% to about 50%, from about 10% to about 45%, from about 10% to about 40%, from about 10% to about 35%, from about 10% to about 30%, from about 10% to about 25%, from about 10% to about 20%, or from about 10% to about 15%).

[0205] DES may be formed by selecting the components of the DES and combining them at an appropriate ratio, preferably with heating. The skilled person will be able to appropriately select a suitable temperature and duration of heating, depending on the components used. Preferably the temperature is above the melting point of at least one of the components, more preferably above the melting point of all of the components. For example, when forming a DES comprising menthol + abietic acid, or thymol + abietic acid, it is preferable that the components are combined and held at a temperature of about 70-80°C for at least one hour, preferably two or more hours.

[0206] If desired, the pH of the DES, or of the composition comprising the DES, may be controlled. This will typically be achieved by using one or more buffering agents as known in the art. A buffering agent is a compound (or mixture of compounds) that resist changes in pH, and typically comprises a mixture of weak acid(s) and weak base(s), for example a mixture of a weak acid and its conjugate base. A wide variety of buffering agents are known in the art, and may be selected depending on the desired application and desired pH. Preferred examples of buffering agents include Good's buffers and organic acids. In some embodiments, the buffering agent is selected from the group consisting of MES, ADA, PIPES, ACES, MOPSO, cholamine chloride, MOPS, BES, TES, HEPES, DIPSO, TAPSO, acetamidoglycine, POPSO, HEPPSO, HEPPS, tricine, Tris, glycinamide, glycylglycine, bicine, TAPS, CHES, borate, acetate, citrate, malate, and phosphate.

[0207] Weak acids such as carboxylic acids may be buffering agents, and accordingly, in some embodiments the terpenoic acid is a buffering agent. In some embodiments, the DES, or the composition comprising the DES, comprises one or more buffering agents.

[0208] In some embodiments, all components of the DES are naturally-occurring. DES in which all components are naturally-occurring are termed natural deep eutectic systems (NaDES). For the avoidance of doubt, a component of a DES is considered to be naturally-occurring if it is chemically identical to a naturally-occurring compound, regardless of whether it was actually obtained from a natural source. For example, a man-made terpenoid that is chemically identical to a naturally- occurring terpenoid is considered to be a naturally-occurring terpenoid.

[0209] In some embodiments, a composition comprises the DES and one or more additional components. Additional components may be selected to alter the properties of the composition. In some embodiments, the one or more additional components are dissolved and / or suspended in the DES. In some embodiments, the one or more additional components form a colloidal suspension with the DES.

[0210] Terpenoids

[0211] Terpenes are a class of plant secondary metabolites derived from two or more isoprene units, and have the formula (CsHs)n for n > 2. Terpenoids are terpenes that been functionalised, modified, substituted, or derivatised. Terpenoids therefore comprise one or more functionalisations, modifications, substitutions, or derivatisations relative to the parent terpene.

[0212] A variety of functionalisations, modifications, substitutions, or derivatisations are possible. In some embodiments, the terpenoid comprises one or more additional oxygen atoms (preferably one or more hydroxyl groups) relative to the parent terpene. In some embodiments the terpenoid differs from the parent terpene in that one or more methyl groups have been moved or removed relative to the parent terpene. In a preferred embodiment, the terpenoid is a hydroxylated terpenoid (i.e. a terpenoid comprising at least one hydroxyl group), more preferably a monohydroxylated terpenoid (i.e. a terpenoid having a single hydroxyl group).

[0213] Terpenoids may be classified according to the number of isoprene units that make up the parent terpene. For example, hemiterpenoids are terpenoids derived from one isoprene unit; monoterpenoids from two; sesquiterpenoids from three; and diterpenoids from four isoprene units.

[0214] In some embodiments, the terpenoid is derived from 1, 2, 3, 4, 5, 6, 7, 8, or more isoprene units, preferably from 1, 2, 3, or 4 isoprene units, more preferably from 2 isoprene units. In some embodiments, the terpenoid is a hemiterpenoid, monoterpenoid, sesquiterpenoid, diterpenoid, sesterterpenoid, triterpenoid, tetraterpenoid, or polyterpenoid; preferably a hemiterpenoid, monoterpenoid, sesquiterpenoid, or diterpenoid; more preferably a monoterpenoid. In a specifically contemplated embodiment, the terpenoid is a monohydroxylated monoterpenoid. Terpenoids may be acyclic or cyclic, i.e. they may contain one or more rings of atoms. In some embodiments, the terpenoid is acyclic, monocyclic, bicyclic, tricyclic, or tetracyclic, or polycyclic; preferably monocyclic.

[0215] In some embodiments, the terpenoid is a volatile compound. Volatile terpenoids readily evaporate at room temperature (e.g. 25°C) and pressure (e.g. 1 atm). Volatility can be assessed by means known in the art, such as by measuring vapour pressure. In some embodiments, the terpenoid has a vapour pressure of at least about 0.001 mmHg at 25°C, such as at least about 0.002, at least about 0.003, at least about 0.004, at least about 0.005, at least about 0.006, at least about 0.007, at least about 0.008, at least about 0.009, at least about 0.01, at least about 0.015, at least about 0.02, at least about 0.03, at least about 0.04, at least about 0.05, at least about 0.06, at least about 0.07, at least about 0.08, at least about 0.09, at least about 0.1, or at least about 0.2, and useful ranges may be selected between any of these values (for example, from about 0.001 to about 0.2, from about 0.001 to about 0.1, from about 0.001 to about 0.09, from about 0.001 to about 0.08, from about 0.001 to about 0.07, from about 0.01 to about 0.2, from about 0.01 to about 0.1, from about 0.01 to about 0.09, from about 0.01 to about 0.08, from about 0.01 to about 0.07, from about 0.015 to about 0.2, from about 0.015 to about 0.1, from about 0.015 to about 0.09, from about 0.015 to about 0.08, or from about 0.015 to about 0.07).

[0216] In some embodiments, the terpenoid is solid at room temperature (for example, at 25°C). In some embodiments, the terpenoid has a melting point of at least about 25°C, such as at least about 26°C, at least about 27°C, at least about 28°C, at least about 29°C, at least about 30°C, at least about 31°C, at least about 32°C, at least about 33°C, at least about 34°C, at least about 35°C, at least about 36°C, at least about 37°C, at least about 38°C, at least about 39°C, at least about 40°C, at least about 41°C, at least about 42°C, at least about 43°C, at least about 44°C, at least about 45°C, at least about 46°C, at least about 47°C, at least about 48°C, at least about 49°C, at least about 50°C, at least about 51°C, at least about 52°C, at least about 53°C, at least about 54°C, at least about 55°C, at least about 56°C, at least about 57°C, at least about 58°C, at least about 59°C, or at least about 60°C, and useful ranges may be selected between any of these values (for example, from about 25°C to about 60°C, from about 25°C to about 56°C, from about 25°C to about 52°C, from about 27°C to about 60°C, from about 27°C to about 56°C, from about 27°C to about 52°C, from about 29°C to about 60°C, from about 29°C to about 56°C, from about 29°C to about 52°C, from about 31°C to about 60°C, from about 31°C to about 56°C, from about 31°C to about 52°C, from about 33°C to about 60°C, from about 33°C to about 56°C, from about 33°C to about 52°C, from about 35°C to about 60°C, from about 35°C to about 56°C, or from about 35°C to about 52°C).

[0217] Some exemplary embodiments of terpenoids include (but are not limited to) aethiopinone, anethole, borneol, bornyl acetate, bisobolol, bulgarene, cadinene, cadinol, calamanene, camphor, carvacrol, carveol, carvone, 1,8-cineole, cinnamaldehyde, citral, citronellal, citronellol, cubeol, dihydrocarveol, eucalpytol, eugenol, farnesol, fenchone, fencholic acid, geraniol, geranyl acetate, oc- ionone, isoborneoljasmone, limonene, linalool, linalyl acetate, menthol, menthone, oc-murool, myristicin, neral, nerol, nerolidol, p-nerediol, ocimene, perillyl alcohol, phenylethyl alcohol, oc- pinene, |3-pinene, polygodial, pulegone, salvipisone, selin-11-en-4-ol, oc-terpinol, terpinen-4-ol, oc- terpinoel, p-terpi nol, thujone, thymol, xanthorrhizol, or isomers or derivatives thereof.

[0218] In a preferred embodiment, the terpenoid is menthol or thymol.

[0219] Terpenoids may be naturally-occurring or synthetic (i.e. man-made). Terpenoids may also be a modified or derivatised form of a naturally-occurring or synthetic terpenoid. For the avoidance of doubt, a terpenoid is considered to be naturally-occurring if it is chemically identical to a naturally- occurring terpenoid, regardless of whether it was actually obtained from a natural source. In other words, a man-made terpenoid that is chemically identical to a naturally-occurring terpenoid is considered to be a naturally-occurring terpenoid. In some embodiments, the terpenoid is a naturally-occurring terpenoid, for example a terpenoid produced by a plant. It will be appreciated that naturally-occurring terpenoids may be used to produce a natural deep eutectic system (NaDES).

[0220] Terpenoids may be found in, or isolated from, a variety of plant species, and can have a variety of useful properties. The terpenoid may be selected based on its properties and the desired properties of the DES. In some embodiments, the terpenoid is a scent compound. In some embodiments, the terpenoid has bioactivity; for example, the terpenoid may be an antioxidant, anti-inflammatory, antimicrobial, antibacterial, antifungal, antiviral, antitumor, anti-insect (such as insecticidal), anti-arachnid (such as arachnidicidal), or a biofouling control compound.

[0221] Terpenoic acid

[0222] A terpenoic acid is a terpenoid that contains a carboxylic acid group. A terpenoic acid may comprise one or more additional functionalisations, modifications, substitutions, or derivatisations relative to the parent terpene. Like terpenoids, terpenoic acids may be classified according to the number of isoprene units that make up the parent terpene. In some embodiments, the terpenoic acid is derived from 1, 2, 3, 4, 5, 6, 7, 8, or more isoprene units, preferably from 3, 4, or 5 isoprene units, more preferably from 4 isoprene units. In some embodiments, the terpenoic acid is a hemiterpenoic acid, monoterpenoic acid, sesquiterpenoic acid, diterpenoic acid, sesterterpenoic acid, triterpenoic acid, tetraterpenoic acid, or polyterpenoic acid; preferably a diterpenoic acid. In a specifically contemplated embodiment, the terpenoic acid is a monocarboxylated diterpenoic acid (i.e. a diterpenoid having a single carboxylic acid group).

[0223] Terpenoic acids may be acyclic or cyclic, i.e. they may contain one or more rings of atoms. In some embodiments, the terpenoic is acyclic, monocyclic, bicyclic, tricyclic, or tetracyclic, or polycyclic; preferably tricyclic.

[0224] In some embodiments, the terpenoic acid is non-volatile. For example, in some embodiments the terpenoic acid has a vapour pressure of less than about 0.2 mmHg at 25°C, such as less than about 0.18, less than about 0.16, less than about 0.14, less than about 0.12, less than about 0.1, less than about 0.08, less than about 0.06, less than about 0.04, less than about 0.02, less than about 0.01, less than about 0.005, or about 0 mmHg at 25°C, and useful ranges may be selected between any of these values (for example, from about 0 to about 0.2, from about 0 to about 0.18, from about 0 to about 0.16, from about 0 to about 0.14, from about 0 to about 0.12, from about 0 to about 0.1, from about 0 to about 0.08, from about 0 to about 0.06, from about 0 to about 0.04, from about 0 to about 0.02, from about 0 to about 0.01, or from about 0 to about 0.005).

[0225] In some embodiments, the terpenoic acid has a melting point of at least about 25°C, such as at least about 50°C, at least about 100°C, at least about 120°C, at least about 140°C, at least about 160°C, at least about 180°C, at least about 200°C, at least about 220°C, at least about 240°C, at least about 260°C, at least about 280°C, at least about 300°C, at least about 320°C, at least about 340°C, or at least about 360°C, and useful ranges may be selected between any of these values (for example, from about 25°C to about 360°C, from about 50°C to about 360°C, from about 100°C to about 360°C, from about 100°C to about 320°C, from about 100°C to about 280°C, from about 100°C to about 240°C, from about 100°C to about 200°C, from about 120°C to about 360°C, from about 120°C to about 320°C, from about 120°C to about 280°C, from about 120°C to about 240°C, from about 120°C to about 200°C, from about 140°C to about 360°C, from about 140°C to about 320°C, from about 140°C to about 280°C, from about 140°C to about 240°C, from about 140°C to about 200°C, from about 160°C to about 360°C, from about 160°C to about 320°C, from about 160°C to about 280°C, from about 160°C to about 240°C, or from about 160°C to about 200°C).

[0226] Some exemplary embodiments of terpenoic acids include (but are not limited to) abietic acid, pimaric acid, sandaracopimaric acid, communic acid, levoprimaric acid, iso-pimaric acid, dehydroabietic acid, neo-abietic, betulinic acid, fencholic acid, moronic acid, oleanolic acid, ursolic acid, or isomers or derivatives thereof.

[0227] Terpenoic acids may be naturally-occurring or synthetic (i.e. man-made). Terpenoic acids may also be a modified or derivatised form of a naturally-occurring or synthetic terpenoid (for example, modified by addition of a carboxylic acid group). For the avoidance of doubt, a terpenoic acids is considered to be naturally-occurring if it is chemically identical to a naturally-occurring terpenoic acids, regardless of whether it was actually obtained from a natural source. In other words, a manmade terpenoic acids that is chemically identical to a naturally-occurring terpenoic acids is considered to be a naturally-occurring terpenoic acids. In some embodiments, the terpenoic acids is a naturally-occurring terpenoid, for example a terpenoic acids produced by a plant. It will be appreciated that naturally-occurring terpenoic acids may be used to produce a natural deep eutectic system (NaDES).

[0228] Terpenoic acids may be found in, or isolated from, a variety of plant species, and can have a variety of useful properties. The terpenoic acid may be selected based on its properties and the desired properties of the DES.

[0229] Sources of terpenoids and terpenoic acids

[0230] Terpenes, terpenoids, and terpenoic acids can be biosynthesised by certain organisms, such as plants. Terpenoids and terpenoic acids are typically first biosynthesised as a terpene, which is then modified (for example by terpenoid synthase enzymes) and / or may undergo further hydrolysis to produce the terpenoid or terpenoic acid.

[0231] Terpenoids and terpenoic acids may be provided by any suitable source, for example from a plant. Terpenoids and terpenoic acids may be present in, and extracted from, a variety of plant tissues such as (but not limited to) branches, heartwood, sap, bark, leaves, fruits, and / or seeds. It is also possible to chemically synthesise terpenoids and / or terpenoic acids, or to chemically modify abundantly available terpenes / terpenoids such as oc-pinene into the desired terpenoid or terpenoic acid. In some embodiments the terpenoid and / or terpenoic acid is present in, or provided by, a plant such as a gymnosperm, preferably a conifer, more preferably a pine, most preferably Pinus radiata. It will be appreciated that the terpenoid and the terpenoic acid need not be from the same source, but may be selected depending on the desired properties of the DES.

[0232] In some embodiments, the terpenoic acid is present in, or provided by, a gymnosperm exudate, preferably a conifer exudate, more preferably pine rosin. In some embodiments, the terpenoic acid is present in, or provided by, tall oil.

[0233] Gymnosperm exudate, conifer exudate, and pine rosin are complex mixtures of compounds including abietic acid and structurally analogous resin acids, and other compounds. In some embodiments, the terpenoic acid is abietic acid.

[0234] The inventors have surprisingly found that unrefined tree exudates may be used directly, without requiring substantial purification. Accordingly, in some embodiments the gymnosperm exudate, conifer exudate, pine rosin, or tall oil is used to form a DES without prior refinement, or with minimal refinement. In some embodiments, the DES comprises two or more compounds present in a gymnosperm exudate, conifer exudate, pine rosin, or tall oil, preferably two or more compounds selected from resin acids such as abietic acid and its isomers, fatty acids, fatty alcohols, and sterols.

[0235] It will be appreciated that the amount of resin acid (such as abietic acid and structural analogues) may vary by species and processing (or lack thereof) of the exudate.

[0236] In some embodiments, the gymnosperm exudate, conifer exudate, or pine rosin comprises at least about 30% by weight of one or more resin acids (such as abietic acid and structural analogues), such as at least about 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or at least about 90%, and useful ranges may be selected between any of these values (for example, from about 30% to about 90%, from about 30% to about 80%, from about 30% to about 70%, from about 40% to about 90%, from about 40% to about 80%, from about 40% to about 70%, from about 50% to about 90%, from about 50% to about 80%, from about 50% to about 70%, from about 60% to about 90%, from about 60% to about 80%, or from about 60% to about 70%).

[0237] In some embodiments, the gymnosperm exudate, conifer exudate, or pine rosin comprises at least about 30% by weight of abietic acid, such as at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, and useful ranges may be selected between any of these values (for example, from about 30% to about 80%, from about 35% to about 80%, from about 35% to about 70%, from about 35% to about 60%, from about 35% to about 50%, from about 40% to about 80%, from about 40% to about 70%, from about 40% to about 60%, from about 40% to about 50%, from about 45% to about 80%, from about 45% to about 70%, from about 45% to about 60%, from about 45% to about 50%, from about 50% to about 80%, from about 50% to about 70%, or from about 50% to about 60%).

[0238] In some embodiments, the terpenoid (or combination of terpenoids) is present in, or provided by, an extract or essential oil (preferably an essential oil) from a plant in the Lamiaceae family, preferably mint or thyme.

[0239] In some embodiments, the terpenoid (or combination of terpenoids) is present in, or provided by, an extract or essential oil from a plant in the Myrtaceae family, preferably from Leptospermum or Eucalyptus plants, and more preferably from L. scoparium.

[0240] In some embodiments, the terpenoid (or combination of terpenoids) is present in, or provided by, an extract or essential oil from a plant in the Rosaceae family.

[0241] Biofouling control compositions

[0242] Many marine antifouling compositions rely on toxic biocides such as cuprous oxide or copper thiocyanate to for their antifouling properties. However, there is increasing concern that these compounds may leach into the marine environment and cause unintended environmental damage.

[0243] Without wishing to be bound by theory, it is believed that biofouling control compositions comprising the DES disclosed herein may be able to provide useful biofouling control properties while reducing or eliminating undesirable environmental damage. Accordingly, described herein is a biofouling control composition comprising, consisting essentially of, or consisting of the DES described herein.

[0244] The biofouling control compositions may be useful in a variety of circumstances where biofouling presents a problem. It is envisioned that the biofouling control compositions will be particularly useful for reducing the biofouling of surfaces that are exposed to water (for example, surfaces that are at least partially submerged). The biofouling control compositions may be useful for surfaces exposed to seawater (such as the ocean), fresh water (such as lakes and / or rivers), and / or brackish water (such as estuaries). It is also envisioned that the biofouling control compositions may be useful for reducing biofouling in other circumstances, such as industrial processing (for example, food processing), medical contexts (for example, hospitals and clinics), and any situation where biofouling poses a problem.

[0245] The skilled person will be able to select appropriate terpenoid(s) and / or terpenoic acid(s) to form a DES for use in a biofouling control composition based on the disclosures of this specification and their common general knowledge. In some embodiments, the biofouling control composition comprises a DES formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoid is selected from the group consisting of bakuchiol, borneol, carvacrol, 1,8- cineole, eugenol, geraniol, hinokitiol, menthol, polygodial, alpha-terpineol, and thymol, and isomers or derivatives thereof. In some embodiments, the at least one terpenoid is selected from the group consisting of aethiopinone, anethole, borneol, bornyl acetate, bulgarene, cadinene, cadinol, calamanene, camphor, carvacrol, carveol, carvone, 1,8-cineole, citral, citronellal, citronellol, cubeol, dihydrocarveol, eucalpytol, eugenol, farnesol, fencholic acid, geraniol, geranyl acetate, oc- ionone, isoborneoljasmone, limonene, linalool, linalyl acetate, menthol, menthone, nerol, nerolidol, ocimene, perillyl alcohol, phenylethyl alcohol, oc-pinene, |3-pinene, polygodial, pulegone, salvipisone, terpinen-4-ol, oc-terpinoel, p-terpinol, thujone, thymol, xanthorrhizol, and isomers and derivatives thereof.

[0246] In some embodiments, the biofouling control composition comprises a DES formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoic acid is selected from the group consisting of abietic acid, pimaric acid, sandaracopimaric acid, communic acid, levoprimaric acid, iso-pimaric acid, dehydroabietic acid, neo-abietic, betulinic acid, moronic acid, oleanolic acid, ursolic acid, and isomers or derivatives thereof.

[0247] In some embodiments, the biofouling control composition comprises the DES and at least one additional component. In some embodiments, the at least one additional component is selected from the group consisting of a binder, a diluent, a viscosity-modifying agent, or an active agent such as an antifouling agent. In some embodiments, the at least one additional component is selected from the group consisting of paraffin, beeswax, propolis, and essential oils and extracts from plants, preferably plants of the Rosaceae, Lamiaceae and / or Myrtaceae families.

[0248] It is envisioned that the biofouling control compositions may be useful for reducing or preventing biofouling on a wide variety of surfaces. Some specific embodiments include watercraft, structures, or articles that are at least partially exposed to water.

[0249] In some embodiments, the biofouling control composition is applied to a surface, preferably a surface that is at least partially submerged when in use. In some embodiments, the surface is a surface of a watercraft or structure. In some embodiments, the biofouling control composition is applied to an article, preferably an article that is at least partially submerged when in use.

[0250] In some embodiments, the watercraft is selected from a boat, ship, dinghy, barge, sloop, or waka.

[0251] In some embodiments, the structure is selected from a mooringjetty, aquaculture infrastructure, or marine-based green energy harvesting infrastructure e.g. wave, tide, wind, or solar energy harvesting infrastructure.

[0252] In some embodiments, the article is selected from a net, rope, mooring, buoy, rigging, and the like.

[0253] The efficacy of a biofouling control composition may be measured using a variety of tests. One such test is a larval settlement test in which the effect of the biofouling control composition on the settlement, metamorphosis, and survival of model biofouling organisms such as the Pacific transparent sea squirt (Ciona savignyl), blue mussel (Mytilus galloprovincialis), and / or Asian kelp (Undaria pinnatifida). One embodiment of this test is presented in Example 3.

[0254] In some embodiments, the biofouling control composition induces a mortality rate of at least about 20% in a biofouling organism (preferably Ciona savignyl, Mytilus galloprovincialis, and / or Undaria pinnatifida) after five days exposure, such as at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 91%, at least about 92%, at least about 93% at least about 94%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, or about 100% mortality. Antimicrobial compositions

[0255] Some terpenoids and terpenoic acids are known to have antimicrobial properties, and therefore the DES disclosed herein may have useful antimicrobial properties. Accordingly, described herein is an antimicrobial composition comprising, consisting essentially of, or consisting of the DES described herein. Also described herein is a method of reducing or preventing microbial growth or survival on a surface, the method comprising applying the DES, or a composition comprising, consisting essentially of, or consisting of the DES, to the surface.

[0256] In some embodiments, the antimicrobial composition is an antibacterial composition, antifungal composition, antiviral composition, or any combination of any two or more of these.

[0257] The skilled person will be able to select appropriate terpenoid(s) and / or terpenoic acid(s) to form a DES for use in an antimicrobial composition based on the disclosures of this specification and their common general knowledge.

[0258] In some embodiments, the antimicrobial composition comprises a DES formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoid is selected from the group consisting of aethiopinone, borneol, bornyl acetate, isoborneol, camphor, carvacrol, dihydrocarveol, (+)-carvone, 1,8-cineole, citral, eucalpytol, eugenol, farnesol, geraniol, geranyl acetate, (+)-limonene, (±)-linalool, menthol, menthone, nerol, perillyl alcohol, oc-pinene, (+)-|3- pinene, salvipisone, (+)-terpinen-4-ol, oc-terpinoel, (-)-thujone, thymol, xanthorrhizol, and derivatives thereof. In some embodiments, the at least one terpenoid is selected from the group consisting of aethiopinone, anethole, borneol, bornyl acetate, bulgarene, cadinene, cadinol, calamanene, camphor, carvacrol, carveol, carvone, 1,8-cineole, citral, citronellal, citronellol, cubeol, dihydrocarveol, eucalpytol, eugenol, farnesol, fencholic acid, geraniol, geranyl acetate, oc-ionone, isoborneoljasmone, limonene, linalool, linalyl acetate, menthol, menthone, nerol, nerolidol, ocimene, perillyl alcohol, phenylethyl alcohol, oc-pinene, |3-pinene, polygodial, pulegone, salvipisone, terpinen-4-ol, oc-terpinoel, p-terpinol, thujone, thymol, xanthorrhizol, and isomers and derivatives thereof.

[0259] In some embodiments, the antimicrobial composition comprises a DES formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoic acid is selected from the group consisting of abietic acid, pimaric acid, sandaracopimaric acid, communic acid, levoprimaric acid, iso-pimaric acid, dehydroabietic acid, neo-abietic, betulinic acid, bonianic acid, oleanic acid, ursolic acid, and derivatives thereof. In some embodiments, the antimicrobial composition comprises the DES and at least one additional component. In some embodiments, the at least one additional component is selected from the group consisting of a binder, a diluent, a viscosity-modifying agent, or an active agent such as an antimicrobial agent. In some embodiments, the at least one additional component is selected from the group consisting of paraffin, beeswax, propolis, and essential oils and extracts from plants, preferably plants of the Rosaceae, Lamiaceae and / or Myrtaceae families.

[0260] The efficacy of an antimicrobial composition may be measured using a variety of tests known in the art.

[0261] It is envisioned that the antimicrobial compositions may be useful for reducing or preventing microbial growth and / or survival on a variety of surfaces. Some specific embodiments include areas where microbial contamination must be avoided, such as hospitals, surgeries, food preparation facilities, and the like. Other embodiments include areas where there is a higher risk of microbial contamination, such as toilets.

[0262] In some embodiments, the antimicrobial composition is applied to a surface, such as a floor, wall, ceiling, door, bench, table, chair, decking, urninal, or toilet.

[0263] Hooves and homes of animals (in particular domestic livestock such as cattle) can be prone to bacterial and / or fungal infections. It is envisioned that the DES and antimicrobial compositions described herein may be useful for reducing the risk of, or preventing, such hoof and / or horn infections. They may also be useful for treating such infections if / when they do occur. Treatment, reduction of risk, and / or prevention may be accomplished by applying suitable DES or compositiosn to the affected area, i.e. the hoof and / or horn to be treated.

[0264] In some embodiments, the DES or the antimicrobial composition is effective against pathogens of apiculture, for example European foulbrood and / or American foulbrood bacteria. In some embodiments, the DES or the antimicrobial composition is effective against bacteria from the Enterococcaceae and / or Paenibacillaceae families, preferably against bacteria from the Melissococcus and / or Paenibadllus genuses, more preferably against Melissococcus plutonius and / or Paenibadllus spp. bacteria. Horticultural and viticultural compositions

[0265] There are a number of circumstances in which a plant such as a tree, shrub, or vine may become wounded, either intentionally or unintentionally. This includes routine horticultural or viticultural practices such as pruning and / or grafting, and wounding by plant pests such as insects. Such wounds may leave the plant particularly vulnerable to infection by microorganisms including bacteria, fungi, and / or viruses. It is desirable to provide compositions for enhancing wound healing in plants and / or for preventing (or reducing the likelihood or severity of) infection in wounded plants.

[0266] The DES disclosed herein may be useful for enhancing wound healing in horticulture and / or viticulture. The DES disclosed herein may also be useful for preventing, or reducing the likelihood and / or severity, of infection in horticulture and / or viticulture. The DES disclosed herein may also be useful for deterring pests in horticulture and / or viticulture.

[0267] Accordingly, disclosed herein is a horticultural and / or viticultural composition comprising, consisting essentially of, or consisting of the DES disclosed herein. Also disclosed herein is a method of improving healing of a plant wound, the method comprising applying the horticultural and / or viticultural composition to the plant wound. Also disclosed herein is a method of preventing, or reducing the likelihood and / or severity of, infection in a plant, the method comprising applying the horticultural and / or viticultural composition to the plant or part thereof. Also disclosed herein is a method of controlling a plant pest, the method comprising applying the horticultural and / or viticultural composition to the plant or part thereof.

[0268] In some embodiments, the horticultural and / or viticultural composition is a horticultural and / or viticultural wound dressing composition. While petroleum-based plant wound dressing compositions have been widely used in the past, it is unclear whether these provide any real benefit to plant healing. Such wound dressings may inhibit the formation of calluses and result in increased risk of decay. Without wishing to be bound by theory, it is believed that a DES formed from plant terpenoids and terpenoic acids, such as are found naturally in plant exudates, may provide superior plant healing without interfering with the natural wound healing process.

[0269] In some embodiments, the horticultural and / or viticultural composition is an antimicrobial composition such as an antibacterial composition, antifungal composition, antiviral composition, or any combination of any two or more of these. In some embodiments, the infection is a microbial infection, such as a bacterial infection or a fungal infection. In some embodiments, the horticultural and / or viticultural composition is a plant pest control composition, such as an insect pest control composition.

[0270] The skilled person will be able to select appropriate terpenoid(s) and / or terpenoic acid(s) to form a DES for use in a horticultural and / or viticultural composition depending on the desired application, based on the disclosures of this specification and their common general knowledge.

[0271] In some embodiments, the horticultural and / or viticultural composition comprises a DES formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoid is an antimicrobial terpenoid. In some embodiments, the antimicrobial terpenoid is selected from the group consisting of aethiopinone, borneol, bornyl acetate, isoborneol, camphor, carvacrol, carveol, dihydrocarveol, (+)-carvone, 1,8-cineole, citral, citronellal, cotronellol, eucalpytol, eugenol, farnesol, geraniol, geranyl acetate, (+)-limonene, (±)-linalool, menthol, menthone, nerol, perillyl alcohol, oc- pinene, (+)-|3-pinene, polygodial, salvipisone, (+)-terpinen-4-ol, oc-terpinoel, (-)-thujone, thymol, xanthorrhizol, and derivatives thereof. In some embodiments, the at least one terpenoid is selected from the group consisting of aethiopinone, anethole, borneol, bornyl acetate, bulgarene, cadinene, cadinol, calamanene, camphor, carvacrol, carveol, carvone, 1,8-cineole, citral, citronellal, citronellol, cubeol, dihydrocarveol, eucalpytol, eugenol, farnesol, fencholic acid, geraniol, geranyl acetate, oc- ionone, isoborneoljasmone, limonene, linalool, linalyl acetate, menthol, menthone, nerol, nerolidol, ocimene, perillyl alcohol, phenylethyl alcohol, oc-pinene, |3-pinene, polygodial, pulegone, salvipisone, terpinen-4-ol, oc-terpinoel, p-terpinol, thujone, thymol, xanthorrhizol, and isomers and derivatives thereof.

[0272] In some embodiments, the horticultural and / or viticultural composition comprises a DES formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoid is a pest deterrent terpenoid. A pest deterrent is a substance that repels a pest species, deters it from feeding and / or reproducing, kills the pest, and / or attracts a pest predator such as a parasitic wasp. A pest deterrent may be a pesticide. In some embodiments, the pest is an insect pest. In some embodiments, the pest deterrent terpenoid is selected from the group consisting of borneol, iso borneol, borynl acetate, iso borynl acetate, camphor, carvone, citronellal, citronellol, eucalyptol, fencholic acid, a- and p-terpinol, and linalool, and derivatives thereof.

[0273] In some embodiments, the horticultural and / or viticultural composition comprises the DES and at least one additional component. In some embodiments, the at least one additional component is selected from the group consisting of a binder, a diluent, a viscosity-modifying agent, a sealant, or an active agent such as an antimicrobial agent (for example an antibacterial and / or antifungal agent), or a pest deterrent agent.

[0274] The efficacy of a horticultural and / or viticultural composition may be measured using a variety of tests known in the art.

[0275] It is envisioned that the horticultural and / or viticultural composition may be useful with a wide variety of plants. Preferred plants are those used by humans, such as food crop plants, fodder or forage plants, ornamental plants, plants grown for biomass, trees, shrubs, and the like.

[0276] In some embodiments, the plant is from an angiosperm plant species. In some embodiments the plant is from a dicotyledonous plant species. Plants that are particularly useful in the methods of the invention disclosed herein include all plants which belong to the superfamily Viridiplantae, in particular monocotyledonous and dicotyledonous plants including a fodder or forage legume, ornamental plant, food crop, tree, or shrub selected from the list comprising Abrus precatorius, Acacia spp., Acer spp., Actinidia spp., Aesculus spp., Allium spp., Arachis duranensis, Arabidopsis spp., Arachis ipaensis, Betula spp., Brassica spp., Buddleja alternifolia, Cajanus cajan, Camellia sinensis, Cannabis spp., Capsicum spp., Carex littledalei, Carica papaya, Carya illinoinensis, Castanea mollissima, Catharanthus roseus, Cephalotus follicularis, Chenopodium quinoa, Cinnamomum cassia, Citrus Clementina, Citrus sinensis, Citrus unshiu, Coffea arabica, Coronillia varia, Corchorus olitorius, Corylus heterophyll, Cotoneaster serotina, Crataegus spp., Cucumis spp., Cupressus spp., Cyathea dealbata, Cydonia oblonga, Cryptomeria japonica, Cymbopogon spp., Dalbergia monetaria, Davallia divaricata, Desmodium spp., Dicksonia squarosa, Diheteropogon amplectens, Dioclea spp, Dolichos spp., Dorycnium rectum, Durio zibethinus, Echinochloa pyramidalis, Ehrartia spp., Eleusine coracana, Eragrestis spp., Erythrina spp., Eucalyptus spp., Euclea schimperi, Eulalia villosa, Fagopyrum spp., Feijoa sellowiana, Fragaria spp., Flemingia spp, Freycinetia banksii, Geranium thunbergii, Ginkgo biloba, Glycine javanica, Glycine max, Glycine soja, Gliricidia spp, Gossypium anomalum, Gossypium barbadense, Gossypium darwinii, Gossypium hirsutum, Gossypium mustelinum, Gossypium raimondii, Gossypium stocksii, Grevillea spp., Guibourtia coleosperma, Hedysarum spp., Helianthus annuus, Hemarthia altissima, Herrania umbratical, Heteropogon contortus, Hevea brasiliensis, Hibiscus syriacus, Hordeum vulgare, Humulus spp., Hyparrhenia rufa, Hypericum erectum, Hyperthelia dissoluta, Indigo incarnata, Ipomoea nil, Ipomoea triloba, Iris spp., Jatropha curcas, Juglans macrocarpa, Juglans regia, Juglans macrocarpa x Juglans regia, Lactuca saligna, Lactuca sativa, Leptarrhena pyrolifolia, Lespediza spp., Lettuca spp., Leucaena leucocephala, Loudetia simplex, Lotonus bainesii, Lotus spp., Lupinus angustifolius, Macadamia integrifolia, Macrotyloma axillare, Malus spp., Manihot esculenta, Medicago sativa, Metasequoia glyptostroboides, Morelia rubra, Morus notabilis, Mucuna pruriens, Musa sapientum, Nicotiana spp., Nelumbo nucifera, Nyssa sinensis, Onobrychis spp., Ornithopus spp., Oryza spp., Panicum hallii, Panicum virgatum, Papaver somniferum, Peltophorum africanum, Pennisetum spp., Persea gratissima, Petunia spp., Phalaenopsis equestris, Phaseolus spp., Phoenix canariensis, Phoenix dactylifera, Phormium cookianum, Photinia spp., Picea glauca, Pinus spp., Pisum sativum, Podocarpus totara, Pogonarthria fleckd' , Pogonarthria squarrosa, Populus spp., Prosopis alba, Prosopis cineraria, Prunus armeniaca, Prunus avium, Prunus dulcis, Prunus mume, Prunus persica Prunus yedoensis var. nudiflora, Pseudotsuga menziesii, Pterolobium stellatum, Punica granatum, Pyrus spp., Quercus spp., Rhamnella rubrinervis, Rhaphiolepsis umbellata, Rhodamnia argentea, Rhododendron griersonianum, Rhododendron simsii, Rhododendron williamsianum, Rhopalostylis sapida, Rhus natalensis, Ribes grossularia, Ribes spp., Ricinus communis, Robinia pseudoacacia, Rosa spp., Rubus spp., Salix spp., Schyzachyrium sanguineum, Sciadopitys verticillata, Sequoia sempervirens, Sequoiadendron giganteum, Solanum chilense, Solanum commersonii, Solanum lycopersicum, Solanum pennellii, Solanum tuberosum, Sorghum bicolor, Spatholobus suberectus, Spinacia spp., Sporobolus fimbriatus, Stiburus alopecuroides, Stylosanthos humilis, Tadehagi spp, Taxodium distichum, Telopea speciosissima, Trema orientale, Tetracentron sinense, Themeda triandra, Theobroma cacao, Trema orientale, Trifolium spp., Triticum spp., Tsuga heterophylla, Vaccinium spp., Vicia spp., Vigna angularis, Vigna radiata var. radiata, Vigna unguiculate, Vitis riparia, Vitis vinifera, Watsonia pyramidata, Zantedeschia aethiopica, Zea mays, Ziziphus jujuba, amaranth, artichoke, asparagus, broccoli, Brussels sprouts, cabbage, canola, carrot, cauliflower, celery, collard greens, flax, kale, lentil, oilseed rape, okra, onion, potato, rice, soybean, straw, sugar beet, sugar cane, sunflower, tomato, squash and tea, amongst others.

[0277] The horticultural and / or viticultural composition may be applied using any suitable technique, for example by spraying, painting, or dipping. The horticultural and / or viticultural composition should be applied to the area where it will have the desired effect. For example, a wound dressing composition will typically be applied to the plant wound and surrounding area; and the pest deterrent composition will typically be applied to the area(s) vulnerable to pest damage such as leaves, shoots, and / or stems. Alternatively, or additionally, in some embodiments the pest deterrent composition may be applied to the area surrounding the plant, and / or to an article that is placed near the plant. Volatile compound-releasing compositions

[0278] Some terpenoids are volatile compounds, and accordingly, in some embodiments the DES may release a volatile compound (such as a volatile terpenoid). Disclosed herein is a composition for releasing a volatile compound, the composition comprising, consisting essentially of, or consisting of the DES. Also disclosed herein is a method of releasing a volatile compound into the air or water, the method comprising contacting the composition, or the DES, and the air or water.

[0279] In some embodiments, the releasing is releasing into air. In some embodiments, the releasing is releasing into water.

[0280] Some terpenes and terpenoids have a pleasant scent and may be used in volatile compoundreleasing compositions intended to release a fragrance into the air, i.e. fragrance-releasing compositions. The DES disclosed herein may therefore be useful for releasing scent compounds such as (but not limited to) the terpenoids from which the DES is formed. Accordingly, described herein is a fragrance-releasing composition comprising, consisting essentially of, or consisting of the DES described herein.

[0281] In some embodiments, one or more components of the DES may be scent compound. For example, terpenoids are the major component of many essential oils. Such terpenoids typically have a pleasant scent and may be used as a component of the DES to produce a fragrance-releasing composition.

[0282] The skilled person will be able to select appropriate terpenoid(s) and / or terpenoic acid(s) to form a DES for use in a volatile compound-releasing composition based on the disclosures of this specification and their common general knowledge. It will be appreciated that volatile terpenoids are preferred for their ability to volatilise and be detected as a scent.

[0283] In some embodiments, the volatile compound-releasing composition comprises a DES formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoid is selected from the group consisting of anethole, borneol, bulgarene, cadinene, cadinol, calamine, camphor, 1,8-cineole, carvacrol, carvone, citral, citronellal, citronellol, cubeol, eucalyptol, eugenol, geraniol, geranyl acetatejasmone, limonene, linalool, linalyl acetate, oc-lonone, menthol, nerol, nerolidol, ocimene, phenethyl alcohol, D-pulegone, terpineol, thujone, thymol, and derivatives thereof. In some embodiments, the at least one terpenoid is selected from the group consisting of aethiopinone, anethole, borneol, bornyl acetate, bulgarene, cadinene, cadinol, calamanene, camphor, carvacrol, carveol, carvone, 1,8-cineole, citral, citronellal, citronellol, cubeol, dihydrocarveol, eucalpytol, eugenol, farnesol, fencholic acid, geraniol, geranyl acetate, oc-ionone, isoborneoljasmone, limonene, linalool, linalyl acetate, menthol, menthone, nerol, nerolidol, ocimene, perillyl alcohol, phenylethyl alcohol, oc-pinene, |3-pinene, polygodial, pulegone, salvipisone, terpinen-4-ol, oc-terpinoel, p-terpinol, thujone, thymol, xanthorrhizol, and isomers and derivatives thereof.

[0284] In some embodiments, the volatile compound-releasing composition may comprise one or more scent compounds in addition to any scent compounds present in the DES. Various scent compounds useful for the production of volatile compound-releasing compositions are known in the art, and may be selected as needed.

[0285] Volatile compound-releasing compositions may be useful to fragrance the air in order to provide a pleasant scent, or to mask unpleasant odours. Volatile compound-releasing compositions are therefore particularly useful in spaces prone to unpleasant odours such as restrooms, gymnasiums, and the like.

[0286] Volatile compound-releasing compositions may be applied to an article that is placed in the space where volatile compound release is desired, or may be applied to one or more surfaces within the space in which volatile compound release is desired. For example, volatile compound-releasing compositions may be applied to walls, ceilings, floors, doors, and the like.

[0287] Some volatile compounds have pest repellent properties. In some embodiments, the volatile compound is a pest repellent compound, preferably an arthropod repellent compound, more preferably an insect repellent compound. For example, the at least one terpenoid may be a pest repellent terpenoid. In some embodiments, the pest repellent terpenoid is selected from the group consisting of borneol, iso borneol, borynl acetate, iso borynl acetate, camphor, carvone, citronellal, citronellol, eucalyptol, fencholic acid, a- and p-terpinol, and linalool, and derivatives thereof.

[0288] Pest control compositions

[0289] Some terpenoids and terpenoic acids are known to have anti-pest properties, such as antiarthropod, anti-insect, and / or anti-arachnid properties. Therefore, the DES disclosed herein may be useful for the control of pests such as arthropods, insects, and / or arachnids. Accordingly, disclosed herein is a pest control composition comprising, consisting essentially of, or consisting of the DES described herein. Also disclosed herein is a method of controlling pests in a treatment area, the method comprising applying the DES, or a composition comprising, consisting essentially of, or consisting of the DES, to the treatment area. Also disclosed herein is an arthropod control composition comprising, consisting essentially of, or consisting of the DES described herein. Also disclosed herein is a method of controlling arthropods in a treatment area, the method comprising applying the DES, or a composition comprising, consisting essentially of, or consisting of the DES, to the treatment area.

[0290] The skilled person will be able to select appropriate terpenoid(s) and / or terpenoic acid(s) to form a DES for use in a pest control composition based on the disclosures of this specification and their common general knowledge. For example, the use of terpenoid(s) and / or terpenoic acid(s) with known anti-pest properties (such as anti-arthropod, anti-insect, and / or anti-arachnid properties) is preferred.

[0291] In some embodiments, the pest is an arthropod pest. In some embodiments, the arthropod is an insect, such as an aphid, beetle, caterpillar, moth, butterfly, bug, thrip, cutworm, weevil, whitefly, grasshopper, locust, ant, termite, flea, louse, cockroach, fly, mosquito, wasp, or hornet. In some embodiments, the arthropod is an arachnid, such as a spider, mite, scabies, or tick.

[0292] In some embodiments, the pest is a worm, a leech, a helminth such as a nematode, or a mollusc such as a snail or slug.

[0293] Controlling pests may comprise repelling or deterring pests from the treatment area; inhibiting the growth of pests (at any or all life stages); reducing the survival of pests; increasing the morbidity of pests; and / or killing pests. In some embodiments, the composition is an pests repellent composition. In some embodiments the composition is an pesticidal composition, such as an arthropodicidal, insecticidal, and / or arachnidicidal composition.

[0294] In some embodiments, the at least one terpenoid is selected from the group consisting of borneol, iso borneol, borynl acetate, iso borynl acetate, camphor, carvone, citronellal, citronellol, eucalyptol, fencholic acid, a- and p-terpinol, and linalool, and derivatives thereof. In some embodiments, the at least one terpenoid is selected from the group consisting of aethiopinone, anethole, borneol, bornyl acetate, bulgarene, cadinene, cadinol, calamanene, camphor, carvacrol, carveol, carvone, 1,8- cineole, citral, citronellal, citronellol, cubeol, dihydrocarveol, eucalpytol, eugenol, farnesol, fencholic acid, geraniol, geranyl acetate, oc-ionone, isoborneoljasmone, limonene, linalool, linalyl acetate, menthol, menthone, nerol, nerolidol, ocimene, perillyl alcohol, phenylethyl alcohol, oc-pinene, p- pinene, polygodial, pulegone, salvipisone, terpinen-4-ol, oc-terpinoel, p-terpinol, thujone, thymol, xanthorrhizol, and isomers and derivatives thereof.

[0295] In some embodiments, the pest control composition comprises the DES and at least one additional component. In some embodiments, the at least one additional component is selected from the group consisting of a binder, a diluent, a viscosity-modifying agent, or an active agent such as an antimicrobial agent. In some embodiments, the at least one additional component is selected from the group consisting of paraffin, beeswax, propolis, and essential oils and extracts from plants, preferably plants of the Rosaceae, Lamiaceae and / or Myrtaceae families.

[0296] The treatment area may be any area in which control of pests is desired. The treatment area may be indoors or outdoors. Exemplary treatment areas include indoor and / or outdoor areas of dwellings (such as homes); food preparation facilities such as kitchens; restaurants; cafes; shops; offices; industrial or commercial buildings; agricultural, horticultural, and / or viticultural facilities; and areas in which plants are grown such as gardens, greenhouses, crop fields, orchards, vineyards, and the like.

[0297] In some embodiments, the composition is applied to a surface within the treatment area, such as a floor, wall, ceiling, door, bench, chair, table, or a surface of a plant. In some embodiments, the composition is applied to an article, which is placed within the treatment area.

[0298] The pest control composition may be applied to the treatment area using any suitable technique, for example by spraying or painting. It may not be necessary to apply the composition to the entire treatment area; for example, it is envisioned that, in some embodiments, pest control compositions may be able to have an effect over a wider area than the immediate area to which they have been applied, by the controlled release of pest control compounds into the air. In some embodiments, the pest control composition is applied to an article that is placed in the treatment area.

[0299] Examples

[0300] 1. Example 1 — NaDES formation

[0301] 1.1 Materials and methods

[0302] The ability of monohydroxy terpenoids such as menthol and thymol to form a NaDES interaction with abietic acid in pine rosin was investigated. Menthol and thymol were obtained at high purity from commercial sources. Purity was confirmed using1H NMR and GC-MS analysis (data not shown).

[0303] Pine rosin is a complex mixture of compounds including abietic acid (AA) and structurally analogous resin acids, and other hydrophobic compounds. The amount of AA and its isomers may vary in different pine rosins from different suppliers. The amount of AA was quantitated using the1H NMR peak integral of a vinyl proton signal (chemical shift = 5.75 ppm) relative to an internal standard (benzene). An analytical standard of AA from Sigma-Aldrich, certified as >80% pure, was used to verify the quantification technique.

[0304] Two commercially-sourced pine rosins contained 47.6 and 49.1% AA, and an additional - 15% of structurally analogous resin acids. Based on these results, it was estimated that resin acids accounted for -65% by weight of the rosin raw materials.

[0305] Rosin was mixed with menthol (M) and thymol (T) individually in a mass range spanning approximately from 6:1 to 1 :3 as shown in Table 1.

[0306] Table 1. Mass and molar ratios of rosin with menthol (M) or thymol (T).

[0307] Ros:T mass Rosin T Resin acids1T AA:T ratio Mass (g) Mass (g) mmols mmols Molar ratio

[0308] 6:1 4.3002 0.7050 9.2 4.7 1.97

[0309] 5:1 4.2073 0.8071 9.0 5.4 1.68

[0310] 4:1 4.0000 1.0220 8.6 6.8 1.26

[0311] 3:1 3.8023 1.3072 8.2 8.7 0.94

[0312] 2:1 3.3058 1.7060 7.1 111.4 0.63

[0313] 1:1 2.5010 2.5095 5.4 16.7 6.32

[0314] 1:2 1.7022 3.3022 3.7 22.0 0.17

[0315] 1:3 1.0099 3.9947 2.2 26.6 0.08

[0316] Ros:M mass Rosin M Resin acids1M AA:M ratio Mass (g) Mass (g) mmols mmols Molar ratio

[0317] 6:1 4.3002 0.7061 9.2 4.5 2.05

[0318] 5:1 4.2073 0.8004 9.0 5.1 1.77

[0319] 4:1 4.0000 1.003 8.6 6.4 1.34

[0320] 3:1 3.8070 1.3061 8.2 8.4 6.98

[0321] 2:1 3.2996 1.7008 7.1 10.9 0.65

[0322] 1:1 2.5011 2.5075 5.4 16.0 0.34

[0323] 1:2 1.7048 3.3028 3.7 21.1 0.17

[0324] 1:3 1.0014 4.0561 2.2 26.0 0.081Molar ratios calculated assuming that resin acids account for 65% of the mass of the rosin. 1.2 Results

[0325] Rosin in its native form is solid and brittle, and menthol and thymol are also solid at room temperature. Therefore, when combinations of these mixtures form single phase liquids, it is indicative of NaDES formation.

[0326] Physical viscosity of both the Ros:T and Ros:M systems decreased with increasing proportions of M / T, with mixtures of solids yielding liquids. Pure rosin was a dark orange solid at room temperature. The 6:1 ratio of Ros:T or Ros:M was a similarly coloured, highly viscous liquid. As the proportion of M or T increased, the colour shifted to a lighter orange and then to a yellow, and the viscosity similarly decreased. Pure menthol was a white solid, and pure thymol was an off-white solid.

[0327] The compositions with Ros:T or Ros:M mass ratios of 2:1, 3:1, and 4:1 were selected for further testing, with corresponding estimated molar ratios of AA:T of 0.63, 0.94, and 1 ,26respectively; and estimated molar ratios of AA:M of 0.65, 0.98, and 1.34 respectively.

[0328] Once formed, NaDES are often highly resilient. For example, it is virtually impossible to break the NaDES formed from the combination of menthol + thymol without dissolution in an appropriate solvent, and neither menthol nor thymol can be recovered under reduced atmosphere pressure in a rotary evaporator or freeze-dryer. The Ros:T and Ros:M NaDES were investigated for similar resilience.

[0329] Microscope slides were coated with Ros:T and Ros:M NaDES at mass ratios of 2:1, 3:1, and 4:1, and placed in a freeze-dryer. Slides coated with thymol or menthol alone were used as a control.

[0330] On the control slides, the M and T evaporated completely, whereas only minimal mass loss was measured in all six coating formulations (Table 2). The formulations with a higher molar excess of M and T (i.e. 2:1) lost more mass than formulations with lower proportions of M or T.

[0331] Table 2. Loss of mass from coated glass slides following freeze-drying (n - 3)

[0332] Coating % weight loss of coating ± standard deviation

[0333] Menthol -100

[0334] Ros:M 2:1 -0.93 ± 0.22

[0335] Ros:M 3:1 0.10 ± 0.34 Ros: M 4:1 0.02 ± 0.11

[0336] Thymol -100

[0337] Ros:T 2:1 -6.35 ± 0.91

[0338] Ros:T 3:1 -0.87 ± 0.15

[0339] Ros:T 4:1 -0.40 ± 0.05

[0340] Infrared (IR) spectroscopy was used to further investigate NaDES formation. Using this technique, the characteristic bands associated with alcohol groups like those found in menthol and thymol can be diagnostic of NaDES formation. Specifically, the O-H stretching vibration — a prominent band between 3500-3000 cm'1— broadens / reduces in intensity relative to the pure compounds in NaDES due to the formation of intermolecular hydrogen bonding networks.

[0341] In our analyses, thymol and menthol alone showed strong O-H stretching vibrations. Rosin alone showed a prominent, broad band corresponding to the C=O stretching band (1690 cm'1).

[0342] In Ros:T and Ros:M NaDES, the O-H stretching peak was broadened / reduced in intensity, and the C=O stretching band had blue shifted by >2 cm'1relative to the rosin spectrum. These features strongly suggest an intermolecular interaction is occurring between carboxylic acid groups in resin acids and alcohol groups in M / T.

[0343] 1.3 Conclusion

[0344] This Example shows that it is possible to form a NaDES from a combination of menthol or thymol and unpurified pine rosin.

[0345] 2. Example 2 — Leaching in seawater

[0346] 2.1 Materials and methods

[0347] NaDES formulations of Ros:T and Ros:M at mass ratios of 2:1, 3:1, and 4:1 were prepared as described in Example 1.

[0348] 2.2 Results

[0349] The solubility of thymol and menthol in seawater was determined by saturating seawater in crystals of both compounds, capping the vials and allowing the systems to equilibrate for 24 h. The average solubility of menthol and thymol in seawater was determined to be 0.66 g L’1and 0.99 g L’1, respectively (data not shown). These results are in line with literature values for both compounds in freshwater. In the case of thymol, this is also in agreement with literature values for solubility in seawater. There was no evidence of vertical partitioning of the compounds within the seawater column.

[0350] In triplicate, glass microscope slides were coated with the Ros:T and Ros:M formulations and placed into 1 L of seawater. Ros:T were coated on only one side, because the leaching rate of T was far greater than for M. Seawater samples were taken at days 1, 2, 5, 8, 12 and 15 for analysis by GC- FID-SPME. After sampling, slides were transferred into fresh seawater (1 L). Leaching rates are presented in Table 3.

[0351] Table 3. Leaching rates of coated glass slides over 15 days ( j.g / cm2 / d yfn= 3 ± standard deviation)

[0352] Day Ros:M 2:1 Ros:M 3:1 Ros:M 4:1 Ros:T 2:1 Ros:T 3:1 Ros:T 4:1

[0353] Day 1 1 489 ± 55 351 ± 83 116 ± 29

[0354] Day 2 2 149 ± 14 92 ± 33 55 ± 14 297 ± 121 188 ± 45 76 ± 5

[0355] Day 3 - 5 4 68 ± 7 49 ± 7 34 ± 7 153 ± 47 112 ± 12 49 ± 9

[0356] Day 6 - 8 7 54 ± 7 40 ± 3 36 ± 6 125 ± 26 97 ± 25 48 ± 11

[0357] Day 9 - 12 11 47 ± 5 43 ± 7 35 ± 5 107 ± 25 121 ± 24 49 ± 14

[0358] Day 15 14 38 ± 7 46 ± 4 36 ± 6 42 ± 24 15 ± 9 6 ± 0

[0359] Both 2:1 formulations leached extensively in the first two days, before the rate gradually came into line with the leaching rates of the 3:1 formulations. At Day 10 leaching rate for the 2:1 formulations were very similar to the rates from the 3:1 formulations. The 4:1 formulations leached at significantly slower rate over the entire time-course.

[0360] 2.3 Conclusion

[0361] This Example shows that NaDES compositions can be used to coat surfaces that are to be submerged in water, wherein they will release an active agent (such as thymol or menthol) over time. 3. Example 3 — Biofouling control activity

[0362] 3.1 Materials and methods

[0363] 3.1.1 Biofouling control efficacy of constituents

[0364] Rosin, menthol, and thymol were assessed for efficacy against marine invertebrate settlement and metamorphosis using the model biofouling taxa the Pacific transparent sea squirt (Ciona savignyi). Broodstock were sourced from Nelson Marina, Nelson, New Zealand and were held in a recirculating seawater system (18 ± 1°C, 33 ± 1 PSU) and fed bulk cultured Isochrysis galbana until ready to spawn. Spawning, fertilisation, and hatching followed methods described previously (Cahill, P. L, Atalah, J., Seiwood, A. I., & Kuhajek, J. M. (2016). Metamorphosis of the invasive ascidian Ciona savignyi: environmental variables and chemical exposure. PeerJ, 4, e1739).

[0365] Just-hatched larvae were used in a bioassay performed in 20-mL glass vials. Vials were filled with seawater containing 50 larvae and spiked with test compounds as necessary to yield the following dilution series:

[0366] • Rosin: 0, 1, 2, 4, 6, 8 pg mL’1

[0367] • Menthol: 0, 0.05, 0.5, 5, 50, 100, 500 pg mL’1

[0368] • Thymol: 0, 0.015, 0.15, 1.5, 15, 30, 60 pg mL’1

[0369] Small amounts of ethanol were used to dissolve the compounds, with final solvent concentrations in the vials not exceeding 10 pL mL’1. There were five replicate vials for each replicate concentration (n = 5), and both blank and solvent controls were included in all cases.

[0370] The assay was setup according to Cahill et al. (2016) with minor modifications to the vials used and total assay volume. Once the assay was initiated, vials were held at 18 ± 1°C in the dark for 5 days. After five days, larvae were inspected and counted using a dissecting microscope. Larvae were scored according to their metamorphic stage, and live and dead larvae were differentiated.

[0371] 3.1.2 Biofouling control efficacy of NaDES

[0372] NaDES formulations of Ros:T and Ros:M at mass ratios of 3:1 and 4:1 were prepared as described in Example 1. The NaDES formulations were assessed for acute effects against model biofouling taxa: the Pacific transparent sea squirt (C. savignyi), the blue mussel (Mytilus galloprovincialis), and the Asian kelp (Undaria pinnatifida).

[0373] At the initiation of the assays, competent larvae of each species were aliquoted into wells with 5 mL of sterilised seawater or double-strength F2 media as appropriate. Wells contained ~35 C. savignyi larvae, ~50 M. galloprovincialis larvae, or - 1000 U. pinnatifida gametophytes, respectively. Three replicate determinations were performed in all instances (n=3), with each species of larvae in a separate set of 3 wells for each NaDES formulation. Plates were incubated for 5 days at 18 ± 1°C, 33 ± 1 PSU, 12:12 light:dark. After 5 days, larvae / gametophytes were inspected and counted using a binocular microscope. Larvae were scored according to developmental stage and as live or dead.

[0374] 3.1.3 Data analysis

[0375] For constituents in aqueous solution, dose-responses were modelled using Weibull or logistic curve fitting as dictated by model fit. Nominal concentration estimates that prevented settlement, metamorphosis, and survival relative to the controls by 50% (LC50) or 99% (LC99) were calculated using R statistical software (Ritz, C., Baty, F., Streibig, J.C., Gerhard, D., 2015. Dose-response analysis using R. PLoS ONE. 10 (12), e0146021).

[0376] Efficacy of the NaDES formulations against C. savignyi, M. galloprovincialis, and U. pinnatifida was calculated as percent mortality from the number of live and dead larvae in each well.

[0377] 3.2 Results

[0378] 3.2.1 Biofouling control efficacy of constituents

[0379] All tested compound inhibited settlement, metamorphosis, and survival of C. savignyi in accordance with sigmoidal dose-response relationships. The LCso and LC99 values are shown in Table 4.

[0380] Table 4. Biofouling control efficacy of individual constituents of NaDES formulations.

[0381] LC50 (pg mL1) LC99 (pg mL1)

[0382] Thymol 3.19 ± 1.98 26.90 ± 3.48

[0383] Menthol 1.43 ± 0.58 5.36 ± 4.17

[0384] Rosin 4.10 ± 0.28 5.16 ± 3.09

[0385] Values shown are mean ± standard error.

[0386] 3.2.2 Biofouling control efficacy of NaDES Larval settlement rates in control wells were high, with 32 ± 10 live C. savignyi larvae, 37 ± 5 live M. galloprovincialis larvae, and 861 ± 107 live U. pinnatifida gametophytes counted in the control wells after 5 days. By comparison, there were no larvae or gametophytes in any of the NaDES coated wells after 5 days and biofouling control efficacy was 100 ± 0% in all instances.

[0387] 3.3 Conclusion

[0388] This Example shows that NaDES can form effective biofouling control compositions.

[0389] 4. Example 4 — Additional NaDES

[0390] 4.1 Materials and methods

[0391] The ability of hydroxy (and oxygenated) terpenoids such as menthol and thymol to form a NaDES interaction with resin acids in pine rosin was further investigated. NaDES were prepared by accurately weighing rosin and terpenoids, heating to 60-160°C for up to five days, and allowing to equilibrate to room temperature. Unless otherwise stated, visual inspection and analyses were performed after allowing NaDES to equilibrate for >4 weeks.

[0392] Five commercial pine rosins (RosA - RosE) and a high purity abietic acid standard (AA) were used to provide resin acids to mixtures. These six materials were characterised with reference to their physical appearance (colour, phase, transparency and viscosity) and acid values by ASTM D664 (Table 5), rosin acid composition by proton nuclear magnetic resonance (1H NMR) spectroscopy (quantitated using benzene internal standard; Pinheiro, A. et aL, 2023, "Rosin from Pinus pinaster Portuguese forests shows a regular profile of resin acids", Frontiers in Plant Science, 14, 1268887; Table 6), and thermophysical properties by differential scanning calorimetry (DSC) (Craveiro et aL, 2016, "Properties and thermal behavior of natural deep eutectic solvents", Journal of Molecular Liquids, 215, 534-540; Table 7).

[0393] Eighteen oxygenated terpenoids were purchased at high purity and their physical appearance was noted (Table 8). For thymol, menthol and carvacrol, purity was confirmed by1H NMR.

[0394] To assess if NaDES can be formed from rosin and structurally variable monoterpenoids (X), each compound in Table 8 was combined at a mass ratio of 2:1 with two different rosins (RosC and RosE). These mass ratios equated to molar ratios ranging from 0.73:1 to 1.09:1 for RosC formulations, and from 0.46:1 to 0.76:1 for RosE formulations (calculated using data from Table 6, and molar mass of 302 for resin acids). Mixtures were visually inspected, and characterised by IR and DSC. They were also subjected to reduced pressure for 1 week, to assess the effect of intermolecular NaDES interactions on evaporation rates compared to pure terpenoids (by gravimetric analysis).

[0395] To assess if NaDES can be formed using compositionally diverse rosins, RosA - RosE (and AA) were combined with thymol at mass ratios of 1 :1 (molar ratio range: 0.5:1 to 1 :1). Mixtures were visually inspected, and characterised by IR and DSC. Viscosity was also measured. Methods were adapted from Nguyen et al., 2020, "Natural deep eutectics as a "green" cellulose cosolvent", ACS sustainable chemistry & engineering, 8(37), 14166-14178 and "Picchio et al.,. "Natural deep eutectic solvents based on choline chloride and phenolic compounds as efficient bioadhesives and corrosion protectors". ACS Sustainable Chemistry & Engineering, 10(2.5), 8135-8142.

[0396] To assess the tuneability of physicochemical properties of NaDES, three hydroxylated monoterpenoids Menthol (M, aliphatic), and Thymol / Carvacrol (T / C, aromatic structural isomers) were mixed with RosD at mass ratios ranging from 1 :9 to 9:1 (molar ratio range: 0.04:1 - 3.2:1). The physical appearance, viscosity, contact angle, and thermophysical properties were measured (as above). These formulations were also coated onto a wide range of substrates, including glass, plastic, wood, and multi-filamentous and / or synthetic materials i.e. nettings.

[0397] RosA:M / T / C NaDES were prepared at mass ratios of 4:1, 3:1 and 2:1 and characterised by IR, assessed for resistance to evaporation at reduced pressure (as above).

[0398] Table 5. Physical appearance and acid values

[0399] RosA RosB RosC RosD RosE AA

[0400] Visual inspection Yellow- Yellow- Yellow- Yellow- Pale Off- brown, brown, brown, brown, yellow, white glassy, glassy, glassy, glassy, solid crystalline powder solid solid solid powder

[0401] Acid value (mg / g KOH) 158 164 170 164 169 188

[0402] Table 6. Rosin acid composition

[0403] Rosin acid Chemical shift (5) RosA RosB RosC RosD RosE AA ppm % w / w % w / w % w / w % w / w % w / w % w / w

[0404] Dehydroabietic 6.893-6.868 (1 H) 4.1 3.5 2.4 2.5 7.9 4.3

[0405] Abietic 5.791 -5.754 (1 H) 60.4 56.9 67.3 62.7 27.2 84.1

[0406] Isopimeric 5.342-5.301 (1 H) 1.3 1.2 0.5 0.1 3.5 0.1

[0407] Sandarapimeric 5.232-5.209 (1 H) 0.2 0.1 0.4 0.2 3.6 0.1

[0408] Levopimeric 0.912-0.907 (3H) 2.1 2.4 1.4 3.0 4.4 3.0 Pimeric 0.795-0.788 (3H) 1.9 6.0 1.7 2.6 5.3 7.6

[0409] Total - 69.9 70.0 73.7 71.0 51.7 99.1

[0410] Table 7. Differential scanning calorimetry (DSC)

[0411] RosA RosB RosC RosD RosE AA

[0412] Tg onset. Onset glass transition temperature (°C) 31.2 31.5 32.2 29.1 30.3 29.6

[0413] Tg, Glass transition temperature (°C) 37.2 35.2 37.5 32.8 34.7 33.4

[0414] Tg end. End glass transition temperature (°C) 43.3 39.5 44.0 38.0 40.0 39.0

[0415] Height_W / g, Height of transition peak (W / g) 0.0 0.0 0.0 0.0 - 0.0

[0416] ACp, Change in heat capacity (J / g.C) 0.4 0.3 0.4 0.3 - 0.3

[0417] Table 8. Oxygenated monoterpenoids and related compounds

[0418] Name Purity (%) CAS No. Physical appearance Melting point (°C)

[0419] Menthol >95% 89-78-1 White crystalline solid 34-36

[0420] Thymol >99% 89-83-8 White crystalline solid 48-51

[0421] Carvacrol >95% 499-75-2 Yellow oily liquid 1

[0422] 4-Carvomenthenol >95% 562-74-3 Pale yellow liquid

[0423] Camphor >95% 76-22-2 White crystalline powder

[0424] Eugenol >98% 97-53-0 Pale yellow liquid -12 - -10

[0425] Geraniol 98% 106-24-1 Pale yellow liquid -15

[0426] Trans, trans-farnesol 96% 106-28-5 Yellow solid <25

[0427] 4-Hexylresorcinol - 136-77-6 Pink powder 66.9

[0428] Cinnamyl alcohol >98% 104-54-1 Faint yellow solid 30-33 p-Anisaldehyde 98% 123-11-5 Colorless liquid -1

[0429] Cuminaldehyde 98% 122-03-2 Yellow liquid 50

[0430] (R)-(-)-Carvone 98% 6485-40-1 Pale yellow liquid 25.2

[0431] (S)-(+)-Carvone 96% 2244-16-8 Pale yellow liquid 25.2

[0432] Citral 95% 5392-40-5 Pale yellow liquid -45.7

[0433] L-Menthone >96% 14073-97- Pale yellow liquid -6

[0434] 3

[0435] L-Fenchone >98% 7787-20-4 Pale yellow liquid -5-6 trans-Anethole 99% 4180-23-8 White, crystalline 20-21 powder 4.2 Results

[0436] Rosin in its native form is a brittle solid, and many monoterpenoids e.g. menthol and thymol, are solid at room temperature (Table 8). Therefore, when mixtures of these compounds form liquids at room temperature, it is indicative of strong deviation from ideal melting point behaviour, and often indicates NaDES formation.

[0437] 4.2.1 NaDES formation with diverse hydroxy terpenoids (and related compounds) Visual inspection

[0438] When mixed with RosC and RosE in a 2:1 mass ratio, all compounds listed in Table 8 (both solids and liquids) formed single phase, flowing, transparent liquids, with a pale colour ranging from pale yellow to orange, at room temperature. For solid monoterpenoids this observation is indicative of NaDES formation i.e. it implies non-ideal melting point behaviour. For liquid monoterpenoids this observation was consistent with NaDES formation.

[0439] The fact that these properties manifested in these media 'off' their eutectic point i.e. in the presence of excess monoterpenoid, excess rosin acid, and / or non-acid rosin components, implies that the residual materials were fully soluble in these media. This property is strongly indicative of the formation of Deep Eutectic Systems (DES) (as defined herein).

[0440] IR spectra

[0441] The IR spectra of the pure alcohols showed relatively sharp and intense O-H stretching bands. In NaDES formulations these bands were less intense and broader, indicating a higher density of vibrational states for O-H groups in the NaDES. There were also small, but significant shifts in the frequency of the C=O stretching band. These observations are consistent with intermolecular interactions such as hydrogen bonding between the terpenoid hydroxy and resin acid carbonyl (for example, carboxylic acid) functional groups. This is strongly indicative of the formation of an extended hydrogen bonding network characteristic of non-ionic Type V NaDES. A summary of the O-H and C=O stretching vibrations for the pure compounds and NaDES formulated with RosE are presented in Table 9.

[0442] Table 9. Summary of O-H and C=O stretching vibrational bands in Rosin E (RosE), pure monoterpenoids (X) and NADES (RosE:X) formulated at a 2:1 from these compounds.

[0443] Pure Compounds NADES (RosE:X) 2:1 u(OH) u(C=O) u(OH) u(C=O) cm'1cm'1cm'1cm'1

[0444] RosE 3424 1690

[0445] Menthol 3268 - 3385br1694

[0446] Thymol 3177 - 3400br1692

[0447] Carvacrol 3360 - 3383br1692

[0448] 4-Carvomenthenol 3437 - 3424br1694

[0449] Camphor - 1738 - 1741,1733,1692

[0450] Eugenol 3472 - 3462br1692 Geraniol 3313 - 3368br1693

[0451] Trans, trans- 3321 - 3410br1693 farnesol 4-Hexylresorcinol 3415, 3332 - 3345br1692

[0452] Cinnamyl alcohol 3482 - 3375br1692 p-Anisaldehyde - 1679 - 1687

[0453] Cuminaldehyde - 1698 - 1693

[0454] (RJ-(-)-Carvone 1668 1693, 1673

[0455] (S)-(+)-Carvone 1668 1692, 1673

[0456] Citral 1671 1718,1692,1673

[0457] L-Menthone - 1706 1708,1693

[0458] L-Fenchone - 1737 - 1735, 1692 trans-Anethole - 1691 br = broad band

[0459] Resistance to evaporation at reduced pressure

[0460] After seven days, under reduced pressure, 100% of all terpenoids listed in Table 8 had evaporated. Under the same conditions, RosE:X formulations lost 1 - 53% of their mass from evaporation. The resistance of these formulations to evaporation is consistent with the formation of strong, intermolecular hydrogen bonding networks commonly associated with formation of Type V NaDES (data not shown).

[0461] Differential Scanning Calorimetry DSC analysis of nine, representative RosE:X samples (prepared at a 2:1 mass ratio) showed no melting points, but all had glass transitions at temperatures below the freezing point of the pure components (Table 10). Only a single glass transition point was observed, and no crystallisation / melting points. These results support the conclusion that these media were also homogeneous, amorphous, glass-forming NaDES. Table 10. Differential scanning calorimetry (DSC) of RosE:monoterpenoid mixtures (2:1 mass ratios).

[0462] NaDES Tg onset Tg Tg end Height ACp

[0463] RosE:Menthol -20.6 -15.4 6.1 0.1 0.8

[0464] RosE:Thymol -25.5 -20.6 -18.4 0.0 0.5

[0465] RosE:Carvacrol -25.8 -22.2 -19.8 0.0 0.5

[0466] RosE:4-Carvomenthenol -27.7 -24.1 -21.9 0.0 0.5

[0467] RosE:Camphor -21.6 -14.9 -10.5 0.0 0.4

[0468] RosE:Eugenol -39.7 -37.3 -32.2 0.0 0.2

[0469] RosE:trans-Anethole -53.5 -50.9 -43.8 0.0 0.2 RosE:4-Hexylresorcinol -11.5 -5.8 -0.1 0.1 0.8

[0470] RosE:Cinnamyl alcohol -35.2 -31.4 -28.1 0.0 0.4

[0471] 4.2.2 NaDES formation with compositionally diverse rosins

[0472] When formulated with T at a 1:1 ratio, all rosins (and AA) formed single phase, flowing, transparent liquids, with a very pale to yellow colouration at room temperature. IR spectra of the mixtures and the pure compounds differed as described in Section 4.2.1.

[0473] Glass transition temperatures for all Ros:T 1 :1 formulations were significantly lower (-41.2 to - 20.3 °C) than pure rosins (32.8 to 37.5 °C) (Tables 7 and 11) . Only a single glass transition point was observed, and no crystallisation / melting points. These results support the conclusion that these media were homogeneous, amorphous, glass-forming NaDES.

[0474] To assess if viscosity could be modified by formulating NaDES using compositionally different rosins, six Ros:T NaDES were formulated at a 1 :1 mass ratio and their viscosities were measured (at 50°C). Viscosity of these NaDES ranged from 81 - 284 cP (Table 11), indicating that different rosins can produce NaDES with different viscosities.

[0475] Table 11. Differential scanning calorimetry (DSC) and viscosity results for mixtures of thymol with five pine rosins (and an abietic acid, AA) standard in 1:1 mass ratios

[0476] RosA:T RosB:T RosC:T RosD:T RosE:T AA:T

[0477] Tg onset. Onset glass transition -35.3 -43.4 -34.8 -38.0 -25.4 -32.2 temperature (°C)

[0478] Tg, Glass transition -32.4 -41.2 -31.1 -35.9 -20.3 -29.5 temperature (°C)

[0479] Tg end. End glass transition -29.4 -37.5 -28.3 -33.1 -18.2 -26.3 temperature (°C)

[0480] Height_W / g, Height of 0.0 0.0 0.0 0.0 0.0 0.0 transition peak (W / g)

[0481] ACp, Change in heat capacity 0.3 0.2 0.3 0.2 0.5 0.3

[0482] (J / g.Q

[0483] Dynamic viscosity (cP) 199 118 81 152 284 177

[0484] 4.2.3 Mass ratio range that form rosin:hydroxyterpenoid Deep Eutectic Systems

[0485] The mass ratio series of RosD:M, RosD:T and RosD:C (1 :9 to 9:1) were visually inspected. Pure rosin was a yellow-brown, glassy solid at room temperature. The 9:1 and 4:1 and 7:3 ratios of RosD:M, RosD:T and RosD:C were darkish orange, highly viscous liquids at room temperature (Table 12). As the proportion of M / T / C increased, colour shifted to increasingly lighter shades of yellow and viscosity visibly decreased. At ratios from 1:1 to 1 :9, M, T and C media were all flowing liquids. The watery appearance of the mixtures increased as the proportion of monoterpenoid increased. These visual characteristics were stable for months for all samples. For specific samples retained for longterm visual observation (Ros:T and Ros:M prepared at 4:1, 3:1 and 2:1 mass ratios) their visual appearance did not changed for over 2 years.

[0486] Unlike rosin, the NaDES formulations could readily be used to coat a range of solid surfaces, including glass, plastic, wood, and plant tissues. Many NaDES formulations could be applied at room temperature with no heating required. Coatings were hydrophobic and strongly resistant to dissolution in both seawater and fresh water. The NaDES formulations were better able to be applied to, and remain adhered to, moving solids (for example, woven fibres like nets) compared to rosin or terpenoids alone.

[0487] Thermophysical properties of the RosD:M, RosD:T and RosD:C (1 :9 to 9:1) series were measured by DSC (Table 11). For formulations of RosD:M and RosD:T with mass ratios of >0.25:1 (e.g. from 0.25:1 to 9:1), a melting point was observed, indicating precipitation and crystallisation of monoterpenoids. At ratios from -0.43:1 to 9:1 (i.e. 3:7 to 9:1) only a glass transition was observed, indicating that these formulations existed as a homogeneous, single phase. For all tested RosD:C ratios, only a glass transition was observed. This observation is consistent with the properties of non-ionic (Type V) NaDES.

[0488] ble 12. Appearance, viscosity, and differential scanning calorimetry of pine rosi hydroxylated monoterpenoid DES.

[0489] Visual inspection Viscosity Differential scanning calorimetry (DSC)

[0490] Mass ratios - (cP 50°C) Tg Height ACp Tc(cold) AHc Tm AHm

[0491] RosD:M 1 :9 (-0.11 :1) Watery, pale yellow liquid - - - - 18.2 9.4 29.9 44.4

[0492] 1 :4 (0.25:1) Watery, pale yellow liquid 10 -43.2 0.0 0.3 -1.2 15.5 23.6 6.5

[0493] 3:7 (-0.43:1) Watery, pale yellow liquid 19 -39.5 0.0 0.2 - -

[0494] 2:3 (-0.67:1) Yellow liquid 39 -35.1 0.0 0.3 - - - -

[0495] 1 :1 Viscous, dark yellow liquid 91 -29.5 0.0 0.3 - -

[0496] 3:2 (1.5:1) Viscous, pale orange liquid 335 -22.3 0.0 0.4 - -

[0497] 7:3 (-2.33:1) Highly viscous, pale orange liquid 1488 -13.1 0.1 0.8 - -

[0498] 4:1 Highly viscous, pale orange liquid 15220 -3.8 0.1 0.9 - -

[0499] 9:1 Highly viscous, dark orange liquid - 9.9 0.1 1.2 - - -

[0500] RosD:T 1 :9 (-0.11 :1) Watery, pale orange liquid - -57.7 0.1 0.8 -15.4 58.1 47.2 95.1

[0501] 1 :4 (0.25:1) Watery, orange liquid 22 -55.1 0.1 0.7 -0.6 59.8 43.9 62.7

[0502] 3:7 (-0.43:1) Watery, orange liquid 40 -51.2 0.0 0.5 - - 41.7 15.6

[0503] 2:3 (-0.67:1) Orange liquid 85 -45.7 0.0 0.3 - - - -

[0504] 1 :1 Viscous, dark orange liquid 201 -38.6 0.0 0.2 - -

[0505] 3:2 (1.5:1) Viscous, dark orange liquid 857 -29.6 0.0 0.4 - -

[0506] 7:3 (-2.33:1) Highly viscous, dark orange liquid 3864 -20.5 0.1 1.0 - - -

[0507] 4:1 Highly viscous, dark orange liquid 50460 -12.4 0.1 0.8 - -

[0508] 9:1 Highly viscous, dark orange liquid - 7.7 0.1 1.0 - - -

[0509] RosD:C 1 :9 (-0.11 :1) Watery, orange liquid - -58.7 0.1 0.8 - -

[0510] 1 :4 (0.25:1) Watery, orange liquid - -55.3 0.1 0.7 - -

[0511] 3:7 (-0.43:1) Watery, orange liquid - -50.7 0.0 0.6 - -

[0512] 2:3 (-0.67:1) Orange liquid - -45.3 0.0 0.4 - - - -

[0513] 1 :1 Viscous, orange liquid - -36.9 0.0 0.2 - -

[0514] 3:2 (1.5:1) Viscous, orange liquid - -29.2 0.0 0.4 - -

[0515] 7:3 (-2.33:1) Highly viscous, orange liquid - -17.6 0.1 0.7 - -

[0516] 4:1 Highly viscous, orange liquid - -8.0 0.1 0.9 - -

[0517] 9:1 Highly viscous, dark orange liquid - 6.1 0.1 0.9 - -

[0518] 4.2.4 Viscosity ranges of Deep Eutectic Systems

[0519] The viscosities of the RosD:M, RosD:T and RosD:C (1 :9 to 9:1 mass ratios) series are reported in Table 12. For practical reasons, measurements were acquired at an elevated temperature (50°C). Viscosity ranged from 10 - 15,220 cP for RosD:M formulations, and from 22 - 50,460 cP for RosD:T formulations (Table 11). For all systems, higher proportions of rosins correlated with higher viscosities in good agreement with visual observations (Table 11). For mixtures of rosin with the solid terpenoids, these results are indicative of NaDES formation. For mixtures of rosin with liquid terpenoid, these results are consistent with NaDES formation.

[0520] 4.2.5 Thermophysical properties of Deep Eutectic Systems

[0521] Rosins (and AA) did not have a melting point, but underwent a glass transition (Tg) at temperatures ranging from 32.8 - 37.5°C (Table 7). The melting points for M, T and C were measured at 34.9, 50.9, 1°C, respectively (Table 8).

[0522] DSC analysis of RosD:M, RosD:T and RosD:C NaDES (1 :9 to 9:1 mass ratios) revealed that they did not have melting points (although samples with excess monoterpenoids did form menthol or thymol crystals during temperature of the DSC analysis), but underwent glass transitions at temperatures far lower than the individual components of these mixtures (Tables 7 and 12). Decreases in Tgwith increasing proportions of monoterpenoids took place in a non-linear fashion, with the best fit equations for these measurements being 2ndorder polynomials (Table 13). This non-linear change in phase behaviour is consistent with non-ideal thermophysical behaviour characteristic of non-ionic (Type V) NaDES.

[0523] Table 3. Equations of second order polynomial fit to plots of the proportion of monoterpenoid (menthol, thymol, carvacrol) in a rosin:monoterpenoid mixture, versus glass transition point (Tg) measured by differential scanning calorimetry of each specific mixture (mixtures spanned mass ratios spanning from 1:9 to 9:1).

[0524] RosD:C RosD:M RosD:T

[0525] Equation y = Intercept + B1*xA1 + B2*xA2

[0526] Intercept 20.21 ± 0.42 19.71 ± 0.52 16.4 ± 3.12

[0527] B1 -147.02 ± 1.88 -130.64 ± 3.00 -158.7 ± 19.28

[0528] B2 65.87 ± 1.74 65.3 ± 3.28 89.39 ± 22.04

[0529] Residual Sum of Squares 33.17 6.15 9170.70

[0530] R-Square (COD) 0.99986 0.99982 0.99087

[0531] Adj. R-Square 0.99982 0.99975 0.98826 4.2.6 Intermolecular interactions by vibrational spectroscopy

[0532] IR spectra of NaDES formulated at a range of mass ratios, using two different rosins (RosD and RosE), and three different hydroxyterpenoids (thymol, carvacrol and menthol) consistently showed broadened / reduced intensity O-H stretching bands relative to pure compounds (Table 14). The carbonyl band was also consistently blue shifted in all formulated NaDES, strongly indicating intermolecular interactions between hydroxyl and carbonyl functional groups in these mixtures. This is consistent with NaDES formation, as discussed in Example 1.

[0533] Table 14. R hydroxyl and carbonyl stretching vibrations of Rosin D (RosD) and Rosin E (RosE)fthymol, menthol, carvacrol and NaDES prepared from these compounds at different mass ratios. u(0H) u(C=O) cm'1cm'1

[0534] Pure compounds

[0535] T (Thymol) 3177 -

[0536] C (Carvacrol) 3360

[0537] M (Menthol) 3268

[0538] RosD 3426 1689

[0539] RosE 3424 1690

[0540] NaDES

[0541] RosD:T 4:6 3406 1691

[0542] RosD:T 5:5 3405 1692

[0543] RosD:T 6:4 3402 1694

[0544] RosE:T 4:6 3400 1691

[0545] RosE:T 5:5 3400 1692

[0546] RosE:T 6:4 3400 1692

[0547] RosD:M 4:6 3380 1694

[0548] RosD:M 5:5 3385 1695

[0549] RosD:M 6:4 3393 1696

[0550] RosD:C 4:6 3356 1691

[0551] RosD:C 5:5 3365 1692

[0552] RosD:C 6:4 3356 1693

[0553] 4.2.1 Hydrophobicity measurements

[0554] To assess if different mass ratios of NaDES affected hydrophobicity, contact angle measurements were taken of RosE:T at three mass ratios: 0.25:1, 1 :1 and 4:1. The contact angle for these formulations were, 38.2, 57.7 and .3°, respectively, indicating that hydrophobicity of these DES could be increasing by increasing the proportion of rosin in the NaDES formulations.

[0555] 4.3 Conclusion This example shows that DES can be formed by combing compositionally diverse rosins with structurally diverse oxygenated terpenoids. It demonstrates that these DES can be functionalised with respect to their viscosity, hydrophobicity and resistance to evaporation, and that these physical properties support the application of these media as coatings on a wide range of substrates. Finally, it shows that excess material in these mixtures e.g. monoterpenoids, resin acids, or other rosin components, are fully miscible with at a wide range of mass / molar ratios, indicative of DES formation.

[0556] 5. Example 5 — Additional leaching in seawater

[0557] 5.1 Materials and methods

[0558] Additional seawater leaching experiments were performed as described in Example 2.

[0559] 5.2 Results

[0560] To assess how much thymol or menthol was lost from coatings over a longer period of time, a leaching rate experiment was conducted. This experiment also investigated differences in release rates depending on rosin acid content. Results are reported in Table 15 as amount of monoterpenoid (thymol or menthol) lost as a percentage of original amount of monoterpenoid present.

[0561] Release rates of menthol and thymol were faster from compositions with higher proportions of monoterpenoids. Release rates were slower from compositions formulated with AA (83.1% w / w abietic acid, 99.1 % w / w total resin acids) than RosD (71.0 % w / w resin acids). By comparison, glass slides coated in menthol and thymol lost all monoterpenoids in less than two weeks under identical conditions. Release rates of menthol were consistently slower than for thymol for equivalent formulations.

[0562] Table 15. Loss of monoterpenoids from NaDES-coated slides to seawater.

[0563] Monoterpenoid loss from coatings (%)

[0564] Days AA:T 2.33:1 RosD:T 2.33:1 RosD:T 4:1 AA:M 2.33:1 RosD:M 2.33:1 RosD:M 4:1

[0565] 0.0 0.1 ± 0.0 0.3 ± 0.1 0.2 ± 0.0 - 0.1 ± 0.0

[0566] 0.1 0.3 ± 0.1 0.4 ± 0.0 0.4 ± 0.1 0.0 ± 0.0 0.1 ± 0.0

[0567] 0.2 0.4 ± 6.1 1.0 ± 6.1 0.6 ± 0.2 0.1 ± 6.1 0.1 ± 6.0 0.1 ± 6.1

[0568] 1 1.4 ± 6.3 3.4 ± 0.7 2.0 ± 6.5 0.4 ± 6.2 0.6 ± 6.1 6.4 ± 6.2

[0569] 2 2.3 ± 0.2 5.3 ± 1.0 2.9 ± 0.9 0.4 ± 0.0 0.9 ± 0.1 0.7 ± 0.4

[0570] 3 2.7 ± 0.1 6.7 ± 0.1 4.6 ± 0.8 1.2 ± 0.2 1.6 ± 0.1 1.2 ± 0.2

[0571] 5 4.1 ± 0.3 8.8 ± 0.8 6.5 ± 0.8 1.6 ± 0.4 2.3 ± 0.2 1.4 ± 0.3

[0572] 7 5.4 ± 0.4 10.4 ± 0.2 8.5 ± 0.4 2.1 ± 0.3 3.2 ± 0.5 1.8 ± 0.2 14 8.0 ± 0.7 16.4 ± 0.1 10.7 ± 0.3 3.9 ± 0.6 5.3 ± 0.7 3.3 ± 0.7

[0573] 21 9.5 ± 1.1 19.3 ± 1.6 13.1 ± 1.5 5.0 ± 0.7 7.5 ± 0.7 4.4 ± 0.8

[0574] 42 14.0 ± 1.0 26.8 ± 0.1 18.6 ± 0.6 7.7 ± 1.5 10.1 ± 1.4 6.2 ± 1.1

[0575] 63 14.2 ± 2.1 28.6 ± 1.3 20.1 ± 1.3 10.5 ± 1.6 12.8 ± 1.3 8.2 ± 1.7

[0576] Values shown are average of three replicates ± standard deviation. Values are amount of monoterpenoid lost as a percentage (w / w) of the amount of monoterpenoid originally present.

[0577] 5.3 Conclusion

[0578] This Example shows that NaDES compositions can be used to coat surfaces submerged in water, wherein they will release an active agent (such as thymol or menthol) over time. It also shows that the release rate of the active agent can be altered by formulating at different mass ratios, using rosins with different compositions, and using structurally different monoterpenoids.

[0579] 6. Example 6 — Additional biofouling control activity

[0580] 6.1 Materials and methods RosD:T and RosD:M NaDES formulated at mass ratios of 3:1 and 4:1 were prepared as described in Example 4 and coated onto glass microscope slides. Slides were added to falcon tubes containing seawater (50 mL). After 48 h the leachate was recovered and serially diluted for use in bioassays. Concentrations of abietic acid (and isomers), thymol and menthol in the leachate were quantitated by LC-MS, LC-UV and GC-FID, respectively (Table 16). Table 6. Concentrations of Biofouling control efficacy of individual constituents of NaDES formulations.

[0581] RosD:T 3:1 RosD:T 4:1 RosD:M 3:1 RosD:M 4:1

[0582] Abietic Thym Abietic Thym Abietic Menth Abietic Menth acid ol acid ol acid ol acid ol ug / mL ug / m ug / mL ug / m ug / mL ug / mL ug / mL ug / mL

[0583] L L

[0584] Leachate 17.2 89.4 16.2 58.2 20.9 62.5 20.0 32.2

[0585] 48 h

[0586] Dilution 1 9.7 44.5 8.1 29.6 9.0 32.6 10.8 13.9

[0587] Dilution 2 4.0 22.5 3.9 14.2 5.5 12.3 4.3 6.7

[0588] Dilution s 1.5 6.8 1.3 4.2 1.9 5.4 1.7 1.9

[0589] Dilution 4 0.4 1.3 0.3 0.7 0.0 1.1 0.3 0.4

[0590] Dilution 5 0.2 0.6 0.1 0.5 0.2 6.4 0.2 0.3

[0591] Dilution 6 0.1 0.3 0.1 0.3 0.0 0.3 0.1 0.0

[0592] Dilution 7 0.1 0.2 0.0 0.1 0.0 0.0 0.0 0.0

[0593] Dilution s 0.4 1.2 0.3 - 0.3 0.0 0.3 0.0

[0594] Dilution s 0.2 0.5 0.4 0.4 0.1 0.0 0.1 1.6

[0595] Dilution 10 0.0 0.3 0.1 0.1 0.0 0.0 0.0 0.0 Dilution 11 0.0 6.1 0.0 0.1 0.0 0.0 0.0 6.0

[0596] The ability of the leachates to inhibit biofilm formation and kill a marine bacterium (Tenadbaculum maritimum) were assessed by Crystal Viloet assay and bacterial viability assay using LIVE / DEAD™ stain using methods modified from O'Toole G.A. (2011, "Microtiter Dish Biofilm Formation Assay", J. Vis. Exp., 30(47), 2437, doi: 10.3791 / 2437) and a standard UV assay, respectively.

[0597] The ability of the leachates to inhibit reproduction / growth and viability of a marine diatom (Cylindrotheca dosterium) were assessed using a biomass estimation (chlorophyll by UV) and diatom viability assay using SYTOX™ green nucleic acid stain using methods described by Venkatnarayanan et al. (2017, Mar Pollut. Bull. 2017 Nov 30;124(2):819-826. doi: 10.1016 / j.marpolbul.2016.12.059).

[0598] The ability of the leachates to inhibit settlement of Ciona savignyi was assessed using methods described in Example 4 and Cahill et al. (2016, "Metamorphosis of the invasive ascidian Ciona savignyi: environmental variables and chemical exposure", PeerJ, 4, doi: 10.7717 / peerj.1739).

[0599] The ability of the leachates to inhibit settlement of Mytilus edulis were assessed using methods described by Grant et al. (2022, "Effect of regio- and stereoisomerism on antifouling 2,5- diketopiperazines", Organic & Biomolecular Chemistry. 20. doi: 10.1039 / D20B01864K).

[0600] Data from these assays were used to calculate concentrations that could effectively inhibit growth (EC50) and kill (LC50) these organisms in seawater.

[0601] 6.2 Results

[0602] EC50 and LC50 of leachates marine fouling organisms are summarised in Table 17.

[0603] Table 17. Effective (EC50) and lethal (LC50) concentrations of leachates from Ros:M and Ros:T NaDES coatings against four marine fouling organisms.

[0604] Bacteria Diatom Ascidian Bivalve

[0605] T. maritimum C. dosterium C. savignyi M. edulis

[0606] EC50 LC50 EC50 LC50 EC50 LC50 EC50 LC50 pg / mL pg / mL pg / mL pg / mL pg / mL pg / mL pg / mL pg / mL

[0607] Ros:T 3.6 1.8 12.3 22.1 1.2 1.4 1.7 2.9

[0608] 3:1

[0609] Ros:T 8.4 8.3 9.9 27.0 1.4 1.0 2.8 3.9

[0610] 4:1 Ros:M 17.5 11.1 42.2 16.0 4.3 6.5 2.7 6.3

[0611] 3:1

[0612] Ros:M 9.1 11.1 3.9 10.8 1.9 1.5 9.3 1.9

[0613] 4:1

[0614] Rosin 55.8 65.7 203.7 14.9 2.7 1.2 3.2 1.5

[0615] 6.3 Conclusions

[0616] This Example shows that NaDES can form effective marine antifouling compositions.

[0617] 7. Example 7 — Control of Varroa mites

[0618] 7.1 Materials and methods

[0619] Rosimthymol NaDES (Ros:T) were prepared by accurately combining a commercial rosin 'Ros_D' (71% resin acids by mass, by 1 H NMR) with thymol at a mass ratio of 2:1 (molar ratio = 1.07:1). In triplicate, this viscous liquid was coated onto glass microscope slides (7.5 x 2.6 cm). The dose of thymol was controlled by varying the amount of coating applied. Six different doses of thymol were assessed, ranging from 50 - 500 mg.

[0620] To assess the relative efficacy of miticides the apiarium bioassay of Bahreini et al. was followed (Bahreini et al., 2021, "New bioassay cage methodology for in vitro studies on Varroa destructor and Apis mellifera", PLoS One, 16(4), doi: 0.1371 / journal.pone.0250594). Briefly, the apiariums consisted of inverted 1000 mL plastic containers with a #7 plastic mesh base. Samples of ~ 150 honey bees were enclosed in the apiarium and the test compounds were applied. During the assay, varroa mites dislodged via grooming or exposure to miticides fell through the mesh floor onto a piece of sticky board where they were immobilised. The assay was run for 5 hours with regular counts of mite fall. Bee mortality was also assessed by counting the number of dead bees on the floorboard. At the end of the assay, the honey bees were frozen and any remaining varroa mites dislodged by an ethanol wash for counting.

[0621] Mixed-aged bees were collected from the brood frames of Varroa- infested (varroa infestation >3%) colonies. Each treatment was run in triplicate. Mite mortality in each treatment was estimated by dividing the mites counted on the stickyboards by total mites in the apiarium (mites on stickyboards + mites in ethanol wash). A mixed model (ANOVA) was used to analyse differences in mite mortality data.

[0622] 7.2 Results Varroa destructor is an arachnid parasite of honey bees (Apis mellifera). Honey bee colonies that are not managed for varroa typically fail within 18 months. NaDES compositions were tested for their ability control Varroa mites and compared with commercially available products Apivar® and Thymovar®. Mite mortality for the different treatments is shown in Table 18.

[0623] Table 18. Varroa mite mortality in aparium-based bioassay

[0624] Treatment Mite mortality (%)

[0625] Negative control 1 ± 3a

[0626] Positive control — Apivar® (100 mg amitraz) 49 ± 11b

[0627] Positive control — Thymovar® (-1500 mg thymol) 33 ± 3b

[0628] RosD:T 2:1 (500 mg thymol) 39 ± 6b

[0629] RosD:T 2:1 (400 mg thymol) 29 ± 2b

[0630] RosD:T 2:1 (300 mg thymol) 33 ± 2b

[0631] RosD:T 2:1 (200 mg thymol) 44 ± 8b

[0632] RosD:T 2:1 (100 mg thymol) 22 ± 15c

[0633] RosD:T 2:1 (50 mg thymol) 1 ± 2a

[0634] Values shown are the average of three replicates ± standard deviation. Treatments that do not share a letter are significantly different (p < 0.05).

[0635] NaDES formed from a mixture of rosin and thymol produced significantly higher mite mortality than the negative control at all concentrations except the lowest. The NaDES also produced mite mortality that was not significantly different from a commercial thymol-based product, even at much lower concentrations of thymol.

[0636] Conclusion

[0637] This example shows that NaDES can form effective pest control compositions, such as arthropod control compositions,

[0638] 8. Example 8 — Antimicrobial wound dressing

[0639] 8.1 Materials and methods

[0640] Agar plates were inoculated on one side with Eutypha lata (both infected plant tissue (plugs) and spores) and Botryosphaeria (spores). On the other side of the plate, rosin, thymol, carvacrol, menthol or NaDES formulations (RosD:M, RosD:T, and RosD:C prepared at a 2:1 mass ratio as described in Example 4) were added. Inhibition of fungal growth was determined by physical measurement of uninfected agar. Measurements were taken after 1 and 8 weeks (E. lata plugs and Botryosphaeria spores) and after 1 and 16 weeks (Botryosphaeria plugs). All analyses were replicated five times.

[0641] To assess how diffusion rates of thymol differed between the neat compounds and NaDES formulations, the following experiment was performed. In the centre of agar plates, thymol (neat, 5 mg) and thymol (formulated in Ros:T, 2:1, 15 mg) were loaded i.e. for a total load of 5 mg in both. Thymol was allowed to diffuse and samples were taken at 10, 25, and 40 mm from the centre point of the plate at Day 1, 3, and 8. All samples were collected in triplicate. Thymol concentration of the agar samples were measured by GC-FID as described in Example 2, with results reported in pg-g"1of agar.

[0642] 8.2 Results

[0643] Diffusion rates form the pure thymol were generally faster than from the NaDES formulation, as shown in Table 19.

[0644] Table 19. Diffusion rates of thymol and NaDES (Ros:T, 2:1 mass ratio) in agar

[0645] Values shown are averages of three replicates ± standard deviation.

[0646] Agar plates containing pure thymol inhibited fungal growth on >88% of the agar plate area for up to 8 weeks (Table 20). Ros:C and Ros:T inhibited growth of E. lata (plugs) by >65% of the inoculated agar plate area for at least 8 weeks. The same formulations inhibited growth of Botryosphaeria (spores) by >69% and Botryosphaeria (plugs) by >86% for one week. After 8 weeks bacterial Botryosphaeria growth was still inhibited around both the spores and the plugs, but the zone of growth inhibition had shrunk to 3% - 5% for Ros:C, and 13 - 24% for Ros:T (Table 20).

[0647] Table 20. Inhibition of fungal growth

[0648] Values shown are averages of five replicates ± standard deviation.

[0649] * Fruiting bodies observed - indicative of stress response to pathogen

[0650] 8.3 Conclusions

[0651] This example shows that NaDES can be used to inhibit the growth of deleterious fungi associated with plant disease. The example also shows that NaDES formulations can reduce the diffusion rate of monoterpenoids from NaDES formulations, relative to the pure compounds.

[0652] 9. Example 9 — Controllable release rates to air

[0653] 9.1 Materials and methods

[0654] Menthol and thymol NaDES formulations were prepared as described in Example 1. Samples (100 - 250 mg) were accurately weighed onto glass slides, which were periodically weighed to determine loss of mass. For several samples, thymol was quantitated by GC-FID to validate the assumption that mass loss was due to the loss of thymol.

[0655] To assess if NaDES formulated using different rosins affected release rates, Ros:T and Ros:M were prepared in a 2:1 mass ratio using RosA, RosB, RosC, and RosD as described in Example 4 with either thymol or menthol, and the rate of weight loss was determined for each (in triplicate).

[0656] To assess if NaDES formulated using different mass ratios affected volatile release rates, RosD:T, RosD:M, AA:T and AA:M were prepared at mass ratios of 1 :2.33, 1 :1, 2.33:1 and 4:1 and the rate of mass loss was determined for each (in triplicate).

[0657] Weight loss from glass slides coated in pure thymol, menthol and rosin were assessed for weight loss in the same way.

[0658] 9.2 Results

[0659] For the four Ros:T 2:1 NaDES prepared with different rosins (A - D), the % weight lost from the NaDES after 15 weeks was in good agreement with amount of thymol lost from the coatings (measured by GC-FID), demonstrating that changes in the mass of the coatings was predominantly due to thymol evaporation. After 14 days all menthol and thymol had evaporated from the slides coated in these compounds. Over the same time period, the mass of the glass slides coated in rosin did not change significantly.

[0660] Thymol and menthol evaporated from the NaDES formulations far more slowly than from glass slides coated in pure menthol and thymol (Table 21). After 13 weeks, only 7.6-26.9% of thymol had evaporated from the Ros:T 2:1 formulations. NaDES formulated with different rosins produced a wide range of release rates, and also different release profiles (Table 21).

[0661] After six weeks 2.8-5.7% of menthol was lost from Ros:M 2:1 formulations. NaDES formulated with different rosins produced different release rates. Menthol was lost at a faster rate than thymol from equivalent formulations (Table 21).

[0662] Menthol and thymol were released at a more rapid rate from NaDES formulated at a 1 :1 mass ratio, than for NaDES formulated at a 2:1 mass ratio. Differences in evaporation rates were observed for rosins with different compositions (Table 22). In some cases, NaDES formulated at a 1 :1 mass ratio produced a single, constant release rate of volatile terpenoids, or a two phase - rapid, then slow - release rate profile.

[0663] Formulating with different mass ratios of rosin produced different release rates. When formulated at 4:1 mass ratios, only 1.2% of thymol and 4.1% of menthol was lost after 9 weeks; formulating at a mass ratio of 2.33:1 resulted in 10.9% of thymol and 7.3% of menthol being lost over the same time period; and formulating at a mass ratio of 1 :2.33 i.e. where menthol and thymol were in excess by mass, resulted in a mass loss of 95.0% of thymol and 90.0% menthol in 9 weeks (data not shown).

[0664] Formulating AA at a 2.33:1 mass ratio resulted in a much slower release rate than for both menthol and thymol, than from Ros:T and Ros:M NaDES at the same concentration. This was also the case for formulations of AA at a 1 :1 mass ratio with menthol and thymol (data not shown). This result shows that higher acid values (and resin acid contents) decreased the release rate of volatiles.

[0665] Table 21. Mass loss (%) of monoterpenoids from NaDES formulated at 2:1 mass ratio.

[0666] Ros:T 2:1 Ros:M 2:1

[0667] Weeks Ros A Ros B Ros C Ros D Ros A Ros B Ros C Ros D

[0668] 1 3.5 ± 0.4 14.1 ± 2.8 2.8 ± 0.5 9.0 ± 2.0 1.4 ± 0.8 2.1 ± 1.2 1.1 ± 0.7 1.4 ± 0.2

[0669] 2 4.8 ± 1.1 15.9 ± 2.6 4.3 ± 0.5 10.5 ± 0.8 1.9 ± 1.1 2.6 ± 1.4 1.8 ± 0.8 2.1 ± 0.1

[0670] 3 5.0 ± 1.1 17.1 ± 3.3 4.9 ± 6.5 11.2 ± 0.6 2.5 ± 1.1 4.2 ± 1.9 2.7 ± 0.9 3.3 ± 0.4

[0671] 4 5.8 ± 1.1 18.5 ± 3.0 5.0 ± 6.2 12.4 ± 1.1 2.7 ± 1.3 4.6 ± 2.5 2.9 ± 0.9 3.6 ± 0.4

[0672] 5 6.5 ± 1.2 19.4 ± 2.7 5.4 ± 0.3 13.2 ± 1.0 2.8 ± 1.0 5.1 ± 2.7 3.1 ± 1.0 3.8 ± 0.3 6 7.0 ± 1.8 20.4 ± 3.0 5.9 ± 0.2 13.6 ± 0.7 2.8 ± 0.9 5.7 ± 0.7 3.3 ± 1.0 4.2 ± 0.3

[0673] 7 7.6 ± 1.5 21.5 ± 3.1 6.3 ± 0.3 14.7 ± 1.0 - - - -

[0674] 8 7.8 ± 1.3 22.7 ± 2.8 6.5 ± 0.5 15.4 ± 1.4 - - - -

[0675] 9 8.8 ± 1.4 23.8 ± 2.6 7.0 ± 0.7 16.4 ± 1.2 - - - -

[0676] 10 8.8 ± 1.4 24.5 ± 2.6 7.0 ± 0.7 16.5± 1.0 - - - -

[0677] 11 8.8 ± 1.4 25.4 ± 2.6 7.3 ±0.2 17.1 ± 1.2 - - - -

[0678] 12 9.2 ± 1.7 26.0 ± 2.8 7.6 ± 6.1 17.5 ± 1.4 - - - -

[0679] 13 9.5 ± 1.7 26.9 ± 2.8 7.6 ± 6.1 17.9 ± 1.4 - - - -

[0680] Values shown are the average of three replicates ± standard deviation. Values are amount of monoterpenoid lost as a percentage (w / w) of amount of monoterpenoid originally present.

[0681] Table 22. Mass loss from NaDES formulated at 1:1 mass ratio.

[0682] Ros:T 1:1 Ros:M 1:1

[0683] Wee Ros A Ros B Ros C Ros D Ros A Ros B Ros C Ros D k

[0684] 1 30.1 ± 35.0 ± 21.0 ± 33.5 ± 34.2 ± 47.9 ± 35.9 ± 42.2 ±

[0685] 2.1 4.2 1.1 2.8 1.9 1.6 2.4 1.8

[0686] 2 47.9 ± 64.9 ± 33.6 ± 57.2 ± 36.4 ± 51.9 ± 39.1 ± 45.4 ±

[0687] 1.3 5.4 1.5 3.9 1.9 0.7 2.6 1.8

[0688] 3 55.2 ± 77.7 ± 36.4 ± 66.7 ± 38.6 ± 53.5 ± 41.3 ± 45.7 ±

[0689] 0.6 2.3 0.8 2.5 2.1 0.8 2.6 2.4

[0690] 4 57.1 ± 80.1 ± 37.8 ± 68.9 ± 39.7± 54.8 ± 43.3 ± 48.6 ±

[0691] 0.5 0.5 1.1 2.3 2.1 0.9 2.8 2.4

[0692] 5 59.2 ± 82.4 ± 39.0 ± 70.9 ± 41.2 ± 55.9 ± 45.6± 49.9 ±

[0693] 0.6 0.7 1.0 2.3 2.3 0.9 3.4 2.2

[0694] 6 61.3 ± 84.8 ± 40.1 ± 72.9 ± 42.6 ± 57.1 ± 47.9 ± 51.3 ±

[0695] 0.2 0.7 0.7 2.0 2.1 1.0 3.4 2.4 Values shown are the average of three replicates ± standard deviation. Values are amount of monoterpenoid lost as a percentage (w / w) of amount of monoterpenoid originally present.

[0696] 9.3 Conclusion

[0697] This Example shows that the release rate of volatile terpenoids can be tuned using rosins with different acid values and resin acid profiles, and by formulating at different mass ratios. It also shows that formulating in this way can produce NaDES with different volatile release profiles, including a two-phase, rapid-then-slow volatile release profile.

[0698] 10. Example 10 — Anti-food pathogen and anti-biofilm applications

[0699] 10.1 Materials and methods Pure carvacrol, thymol, and NaDES (Ros:T and Ros:C formulated at a 2:1 mass ratio, and Ros:T:C formulated at a 2:0.5:0.5 mass ratio) were added to the centre of agar plates in amounts sufficient to provide 5 mg of total terpenoids in each case. All analyses were performed on three different bacterial strains. Agar was formulated specifically to meet the growth requirements of each bacterial pathogen tested. Plates were inoculated with cultures of Listeria monocytogenes (strains 16B01, 15A04 and 15G01) and Vibrio parahaemolyticus (strains 34B02, 37B03 and 48F05) and the radius of growth inhibition zones were measured from the centre of the plate after 48 h.

[0700] Diffusion rates in trypticase soy agar with yeast extract (Listeria) and trypticase soy agar with salt (Vibrio) were measured as described in Example 8.

[0701] To assess NaDES inhibition of biofilm formation, stainless steel (316) tokens (1 cm diameter, 1 mm thickness, food grade finish) were submerged in growth media containing biofilm forming strains of listeria and vibrio for 48 h. After incubation, tokens were transferred to wells containing 2.5 mL of bacteria-specific growth media and 10, 20 and 40 mg of Ros:T or Ros:C formulated at a 2:1 mass ratio. Samples from these wells were taken after 1, 3 and 7 days and the concentration of bacteria in each well were determined by bacterial cell count assays.

[0702] 10.2 Results

[0703] Monoterpenoids diffused through both types of agar more rapidly from pure compounds than from formulated NaDES Table 23, results in line with those described in Example 8).

[0704] Table 23. Diffusion rates of thymol and NaDES (Ros:T, 2:1 mass ratio) in agar

[0705] Values shown are averages of three replicates ± standard deviation.

[0706] All NaDES formulations inhibited growth of all strains to a similar extent. Larger zones of inhibition were measured for the pure compounds (Table 24). There was no significant difference between the effectiveness of NaDES formulated with thymol, carvacrol, and both. Table 24. Growth inhibition of Vibrio (n~3) and Listeria strains (n=3) by thymol, menthol and NaDES after 48 h

[0707] Vibrio Listeria

[0708] Radius of zone of inhibition (mm)+

[0709] Thymol 52 ± 8 52 ± 3

[0710] Carvacrol 43 ± 7 48 ± 5

[0711] Ros:T 2:1 31 ± 3 34 ± 6

[0712] Ros:C 2:1 26 ± 8 32 ± 1

[0713] Ros:T:C 2:0.5:0.5 29 ± 2 33 ± 4

[0714] +Zone of inhibition is an average of 3 strains of L. monocytogenes and V. parahaemolyticus.

[0715] NaDES (2:1 Ros:T) at all three concentrations reduced all biofilm-forming bacterial strains below the levels of detection after a single day, with two exceptions. The lowest dose of Ros:T (10 mg) left a small amount (0.03% of untreated control wells) of Vibrio 37E03 cells alive after 1 day, and all three doses of Ros :T left a small amount (0.08 - 0.34% of untreated control wells) of Vibrio 48F05 after one day. After three days all wells were completely sterilised.

[0716] 10.3 Conclusion

[0717] NaDES formulations modify diffusion of hydroxylated terpenoids in aqueous media (agar), inhibiting growth and biofilm formation of both gram positive and gram negative pathogenic bacteria.

[0718] Industrial application

[0719] The disclosure relates to a deep eutectic system (DES) formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoic acid is present in a gymnosperm exudate. Biofouling control, antimicrobial, horticultural, viticultural, and arthropod and / or pest control compositions comprising the DES are also provided, as are compositions for releasing a volatile compound.

Claims

WE CLAIM:

1. A deep eutectic system (DES) formed from at least one terpenoid and at least one terpenoic acid, wherein the at least one terpenoic acid is present in a gymnosperm exudate.

2. The DES of claim 1, wherein the at least one terpenoic acid comprises at least one resin acid, preferably a diterpenoic acid, more preferably abietic acid or an isomer or derivative thereof.

3. The DES of any previous claim, wherein the at least one terpenoid is uncharged.

4. The DES of any previous claim, wherein the at least one terpenoid and the at least one terpenoic acid form non-ionic, non-covalent interactions.

5. The DES of any previous claim, wherein the gymnosperm exudate is a conifer exudate, preferably pine rosin.

6. The DES of any previous claim, wherein the at least one terpenoic acid is provided by tall oil, gum rosin, and / or wood rosin.

7. The DES of any previous claim, wherein the DES comprises two or more compounds present in a gymnosperm exudate.

8. The DES of any previous claim, wherein the DES is formed from the at least one terpenoid and a gymnosperm exudate comprising the at least one terpenoic acid.

9. The DES of any previous claim, wherein the at least one terpenoid comprises an oxygenated terpenoid, more preferably a hydroxylated terpenoid and / or a terpenoid comprising an aldehyde and / or ketone group, most preferably a monohydroxylated terpenoid.

10. The DES of any previous claim, wherein the at least one terpenoid comprises a monoterpenoid.

11. The DES of any previous claim, wherein the at least one terpenoid comprises an antimicrobial compound, such as an antibacterial and / or antifungal compound.

12. The DES of any previous claim, wherein the at least one terpenoid comprises a biofouling control compound.

13. The DES of any previous claim, wherein the at least one terpenoid comprises a scent compound.

14. The DES of any previous claim, wherein the molar ratio of the at least one terpenoid to the at least one terpenoic acid is from about 6:1 to about 1:6, preferably from about 2:1 to about 1:2, more preferably about 1:1.

15. The DES of any previous claim, wherein the viscosity of the DES is from about 100 mPa-s to about 1,000,000 mPa-s for Newtonian fluids within the temperature range of -10 to 60°C, over the shear rate of 0.1 to 10,000 s’1.

16. The DES of any previous claim, wherein after immersion in water and / or exposure to air for 11 days, the at least one terpenoid is released from the DES at a rate of less than about 500 pg / cm2 / day, preferably less than about 250 pg / cm2 / day, more preferably from about 20 to about 150 pg / cm2 / day.

17. The DES of any previous claim, comprising at least two terpenoids.

18. The DES of any previous claim, comprising at least two terpenoic acids.

19. A method of producing the DES of any previous claim, the method comprising contacting at least one terpenoid and a. at least one terpenoic acid that is present in a gymnosperm exudate; and / or b. at least one resin acid; to produce the DES.

20. A composition comprising the DES of any one of claims 1 to 18 and at least one additional component.

21. A biofouling control composition comprising, consisting essentially of, or consisting of the DES of any one of claims 1 to 18, or the composition of claim 20.

22. A watercraft, structure, or article to which the biofouling control composition of claim 21 has been applied.

23. A method of controlling biofouling of a surface, the method comprising applying the composition of claim 21 to the surface.

24. An antimicrobial composition, such as an antibacterial, antifungal, and / or antiviral composition, comprising, consisting essentially of, or consisting of the DES of any one of claims 1 to 18, or the composition of claim 20.

25. A method of reducing or preventing microbial growth or survival on a surface, the method comprising applying the composition of claim 24 to the surface.

26. The composition of claim 24 or the method of claim 25, wherein the antimicrobial composition has antimicrobial activity against one or more bacterial pathogens, preferably from the genus Vibrio and / or Listeria.

27. A horticultural and / or viticultural composition comprising, consisting essentially of, or consisting of the DES of any one of claims 1 to 18, or the composition of claim 20.

28. A method of improving healing of a plant wound, the method comprising applying the composition of claim 27 to the plant wound.

29. A composition for releasing a volatile compound into air, the composition comprising, consisting essentially of, or consisting of the DES of any one of claims 1 to 18, or the composition of claim 20.

30. A method of releasing a volatile compound into air, the method comprising contacting the composition of claim 29, and the air.

31. The composition of claim 29, or the method of claim 30, wherein the volatile compound is a scent compound.

32. The composition of claim 29, or the method of claim 30, wherein the volatile compound is a pest repellent compound, preferably an arthropod repellent compound, more preferably an insect repellent compound and / or an arachnid repellent compound.

33. An arthropod control composition comprising, consisting essentially of, or consisting of the DES of any one of claims 1 to 18, or the composition of claim 20.

34. A method of controlling arthropods in a treatment area, the method comprising applying the composition of claim 33 to the treatment area.

35. A pest control composition comprising, consisting essentially of, or consisting of the DES of any one of claims 1 to 18, or the composition of claim 20.

36. A method of controlling pests in a treatment area, the method comprising applying the composition of claim 35 to the treatment area.

37. The composition of any one of claims 32, 33, or 35, or the method of any one of claims 34 or 36, wherein the pest or the arthropod is Varroa, preferably Varroa destructor.

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