Oxygen-impermeable porphyrin photosensitizer film composition for application to plants

Abstract

A composition for application to plants is provided. The composition includes a photosensitizer that generates reactive oxygen species in the presence of light and oxygen, the photosensitizer being selected from the group consisting of porphyrins, reduced porphyrins, and combinations thereof; a film-forming agent that forms a film that is substantially impermeable to oxygen when in a non-hydrated state; an antioxidant; and an aqueous carrier in which the photosensitizer, film-forming agent, and antioxidant are solubilized and / or dispersed. The composition is used to improve plant health.

Description

Technical Field

[0001] The technical field generally relates to photodynamic compositions for improving the health of plants, and more specifically to film-forming photodynamic compositions containing photosensitizers applied to plants.

Background Art

[0002] Photodynamic inhibition of microbial pathogens involves exposing a photosensitizing agent to light to generate reactive oxygen species (ROS) such as singlet oxygen that can have a detrimental effect on the microbial pathogen. Photosensitizers typically decompose when in the presence of light and oxygen. There is a need for compositions that can extend the stability of photosensitizers.

Summary of the Invention

[0003] In a first aspect, a composition for application to a plant is provided. The composition comprises a photosensitizer that generates reactive oxygen species in the presence of light and oxygen, wherein the photosensitizer is selected from the group consisting of porphyrins, reduced porphyrins, and combinations thereof; a film-forming agent that is substantially impermeable to oxygen when in an anhydrous state; an antioxidant; and a liquid carrier in which the photosensitizer, the film-forming agent, and the antioxidant are solubilized and / or dispersed.

[0004] In another aspect, the compositions described herein are used to improve the health of plants.

[0005] In yet another aspect, a method for improving plant health is provided. The method includes applying to a plant a composition comprising a photosensitizer that generates reactive oxygen species in the presence of light and oxygen, wherein the photosensitizer is selected from the group consisting of porphyrins, reduced porphyrins, and combinations thereof, a film-forming agent, an antioxidant, and an aqueous carrier in which the photosensitizer, the film-forming agent, and the antioxidant are solubilized or dispersed, and removing at least a portion of the aqueous carrier from the composition for the film-forming agent to form a film on the plant that is substantially impermeable to oxygen when in the non-hydrated state.

[0006] In some implementations, the film-forming agent is selected from the group consisting of ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, hydroxymethylpropyl cellulose, guar gum, hydroxylpropyl cellulose polyvinylpyrrolidone, nanocellulose, soy protein isolate, whey protein, collagen, starch, hydroxypropylated amylomaize starch, amylomaize starch, xylan, polyvinylidene chloride, polyvinyl alcohol (PVOH), ethylene vinyl alcohol (EVA), polyvinyl alcohol copolymers, and combinations thereof.

[0007] In some implementations, the film-forming agent comprises polyvinyl alcohol.

[0008] In some implementations, the polyvinyl alcohol has an average molecular weight of from about 10 kDa to about 200 kDa.

[0009] In some implementations, the polyvinyl alcohol has a degree of hydrolysis of 70% or greater.

[0010] In some implementations, the polyvinyl alcohol has an average molecular weight of from about 50 kDa to about 100 kDa and a degree of hydrolysis of 99% or greater.

[0011] In some embodiments, the antioxidant is more active than the photosensitizer against reactive oxygen species when in solution.

[0012] In some embodiments, the antioxidant is more active than the photosensitizer against reactive oxygen species when in the hydrated film.

[0013] In some embodiments, the antioxidant is selected from the group consisting of vanillin (4-hydroxy-3-methoxybenzaldehyde), o-vanillin (2-hydroxy-3-methoxybenzaldehyde), vanillyl alcohol, tannic acid, gallic acid, propyl gallate, lauryl gallate, carvacrol, eugenol, thymol, sodium lignosulfonate, t-butyl-hydroxyquinone, butylated hydroxytoluene, butylated hydroxyanisole, alpha-tocopherol, D-alpha-tocopheryl polyethylene glycol succinate, retinyl palmitate, beta-carotene, erythorbic acid, sodium erythorbate, sodium ascorbate, ascorbic acid, glutathione, superoxide dismutase, catalase, sodium azide, 1,4-diazabicyclo[2.2.2]octane (DABCO), and combinations thereof.

[0014] In some embodiments, the antioxidant comprises a phenolic antioxidant.

[0015] In some embodiments, the phenolic antioxidant is selected from the group consisting of vanillin (4-hydroxy-3-methoxybenzaldehyde), o-vanillin (2-hydroxy-3-methoxybenzaldehyde), vanillyl alcohol, tannic acid, gallic acid, propyl gallate, lauryl gallate, carvacrol, eugenol, thymol, lignosulfonate, and combinations thereof.

[0016] In some embodiments, the photosensitizer is metallized with a selected metal such that, in response to exposure to light and oxygen, the metallized photosensitizer generates reactive oxygen species.

[0017] In some embodiments, the metal is selected from the group consisting of Mg, Zn, Pd, Al, Pt, Sn, Si, Ga, In, Cu, Co, Fe, Ni, Mn, and mixtures thereof.

[0018] In some embodiments, the metal is selected from the group consisting of Mg(II), Zn(II), Pd(II), Sn(IV), Al(III), Pt(II), Si(IV), Ge(IV), Ga(III), and In(III), Cu(II), Co(II), Fe(II), Mn(II), Co(III), Fe(III), Fe(IV), and Mn(III).

[0019] In some embodiments, the photosensitizer is metal-free and is selected such that upon exposure to light and oxygen, the metal-free photosensitizer generates reactive oxygen species.

[0020] In some embodiments, the photosensitizer includes a reduced porphyrin.

[0021] In some embodiments, the photosensitizer is selected from the group consisting of chlorin, bacteriochlorin, isobacteriochlorin, corrin, corphin, and mixtures thereof.

[0022] In some embodiments, the photosensitizer is chlorin.

[0023] In some embodiments, the chlorin is chlorin e6 or a modified form of chlorin e6.

[0024] In some embodiments, the photosensitizer includes porphyrin.

[0025] In some embodiments, the porphyrin is protoporphyrin or meso-tetra-(4-sulfonatophenyl) porphyrin (TPPS).

[0026] In some embodiments, the photosensitizer comprises protoporphyrin IX (PP IX) or a modified PP IX.

[0027] In some embodiments, the liquid carrier is an aqueous carrier.

[0028] In some embodiments, the aqueous carrier comprises at least one water-soluble compound that increases the solubility and / or dispersibility of at least one of the photosensitizer, film-forming agent, and antioxidant in the aqueous carrier.

[0029] In some embodiments, the aqueous carrier contains oil and is an oil-in-water emulsion.

[0030] In some embodiments, the oil is selected from the group consisting of mineral oil, vegetable oil, and mixtures thereof.

[0031] In some embodiments, the oil comprises a vegetable oil selected from the group consisting of coconut oil, canola oil, soybean oil, rapeseed oil, sunflower oil, safflower oil, peanut oil, cottonseed oil, palm oil, rice bran oil, and mixtures thereof.

[0032] In some embodiments, the oil comprises a mineral oil selected from the group consisting of paraffinic oil, branched paraffinic oil, naphthenic oil, aromatic oil, and mixtures thereof.

[0033] In some embodiments, the oil comprises poly-alpha-olefin (PAO).

[0034] In some embodiments, the composition further comprises a chelating agent.

[0035] In some embodiments, the chelating agent is selected from the group consisting of ethylenediaminetetraacetic acid (EDTA) or an agriculturally acceptable salt thereof, ethylenediamine-N,N'-disuccinic acid (EDDS) or an agriculturally acceptable salt thereof, iminodisuccinic acid (IDS) or an agriculturally acceptable salt thereof, nitrilotriacetic acid (NTA) or an agriculturally acceptable salt thereof, L-glutamic acid N,N-diacetic acid (GLDA) or an agriculturally acceptable salt thereof, methylglycine diacetic acid (MGDA) or an agriculturally acceptable salt thereof, diethylenetriaminepentaacetic acid (DTPA) or an agriculturally acceptable salt thereof, ethylenediamine-N,N'-diglutaric acid (EDDG) or an agriculturally acceptable salt thereof, ethylenediamine-N,N'-dimaleic acid (EDDM) or an agriculturally acceptable salt thereof, 3-hydroxy-2,2-iminodisuccinic acid (HIDS) or an agriculturally acceptable salt thereof, hydroxyethyliminodiacetic acid (HEIDA) or an agriculturally acceptable salt thereof, polyaspartic acid, and mixtures thereof.

[0036] In some embodiments, the chelating agent is metallized.

[0037] In some embodiments, the chelating agent is metal-free.

[0038] In some embodiments, the composition further comprises a surfactant.

[0039] In some embodiments, the surfactant is selected from the group consisting of ethoxylated alcohols, polymeric surfactants, fatty acid esters, polyethylene glycols, ethoxylated alkyl alcohols, monoglycerides, alkyl monoglycerides, and mixtures thereof.

[0040] In some embodiments, the film-forming agent is present in an amount of about 0.01 wt% to about 20 wt% based on the total weight of the composition.

[0041] In some embodiments, the photosensitizer is present in an amount of about 0.01 wt% to about 10 wt% based on the total weight of the composition.

[0042] In some embodiments, the antioxidant is present in an amount of about 0.01 wt% to about 5 wt% based on the total weight of the composition.

[0043] In some embodiments, the composition is a composition that can be used immediately upon application to the plant.

[0044] In some implementations, the composition is a concentrate that is diluted before being applied to the plant.

[0045] In some embodiments, the plant is a grown plant.

[0046] In some embodiments, the plant is a non-woody crop plant, a woody plant, or turfgrass.

[0047] In some embodiments, the film is substantially impermeable to oxygen when in an environment with a relative humidity lower than about 50% RH.

[0048] In some embodiments, the film is substantially impermeable to oxygen when in an environment with a relative humidity lower than about 60% RH.

[0049] In some embodiments, the film is substantially permeable to oxygen when in a hydrated state.

[0050] In some embodiments, the film is substantially permeable to oxygen when in an environment with a relative humidity of 50% RH to 100% RH.

[0051] In some embodiments, the film is substantially permeable to oxygen when in an environment with a relative humidity of 60% RH to 100% RH.

[0052] In some embodiments, the composition is for applying to the plant by at least one of irrigation, spraying, misting, scattering, injection, and dipping.

[0053] In some embodiments, the composition is applied to non-renewable parts of plants.

[0054] In some embodiments, the liquid carrier is removed by air drying after the composition has been applied to the plant.

[0055] In some embodiments, the film-forming agent forms a film when at least a portion of the liquid carrier is removed from the composition.

[0056] In some embodiments, the composition is for use in promoting the health of plants.

[0057] In some embodiments, promoting the health of plants includes preventing or inhibiting the growth of microbial pathogens of the plants.

[0058] In some embodiments, the microbial pathogens include fungal pathogens, bacterial pathogens, viruses, viroids, virus-like organisms or phytoplasmas.

[0059] In some embodiments, the microbial pathogen is a fungal pathogen.

[0060] In some embodiments, the microbial pathogen is a bacterial pathogen.

[0061] In some embodiments, promoting the health of plants includes increasing the resistance of the plants to one or more abiotic stresses.

[0062] In some embodiments, the one or more abiotic stresses are selected from the group consisting of low temperature stress, heat stress, water stress, transplant shock stress, low light stress, oxidative stress, drought stress and salt stress.

[0063] In some embodiments, promoting the health of plants includes controlling insect pests of the plants.

[0064] In some embodiments, the insect pest is selected from the group consisting of insects and insect larvae.

Brief Description of the Drawings

[0065]

Figure 1

Modes for Carrying Out the Invention

[0066] Photodynamic inhibition of microbial pathogens and / or insects that may parasitize plants can be achieved by applying a photosensitizer compound. The photosensitizer compound reacts to light by generating reactive oxygen species (ROS). The photosensitizer compound can also be used to increase the resistance of plants to damage caused by one or more abiotic stresses. The ROS generated by the photosensitizer are active enough to help inhibit microbial pathogens and / or insects on the plant, while they are also typically active enough to decompose the photosensitizer compound. Therefore, there is a need to stabilize the photosensitizer compounds so that they are stable enough to be applied to plants and generate ROS for a sufficient time to effectively promote the health of the plants.

[0067] This disclosure provides a film-forming combination and composition for application to plants, comprising a photosensitizer that generates reactive oxygen species in the presence of light and oxygen, a film-forming agent, and an aqueous carrier. The film-forming composition can also include an antioxidant. The photosensitizer is selected from the group consisting of porphyrins, reduced porphyrins, and combinations thereof. The film-forming agent can be a film-forming polymer such as polyvinyl alcohol. The film-forming agent forms a film that is substantially impermeable to oxygen when at least a portion of the aqueous carrier is removed after application to the plant. The antioxidant can be a phenolic antioxidant. The photosensitizer, film-forming agent, and antioxidant are solubilized and / or dispersed in the aqueous carrier. In one implementation, the photosensitizer compound is a porphyrin or reduced porphyrin compound such as a chlorin compound.

[0068] Exemplary porphyrin compounds are protoporphyrin IX or a modified form of protoporphyrin IX or an agriculturally acceptable salt thereof. Exemplary chlorin compounds are chlorophyllin, a modified form of chlorophyllin, or an agriculturally acceptable salt thereof.

[0069] More details regarding the photosensitizer, film-forming agent, and other components of the film-forming composition, as well as methods for preparing such compositions, are provided in this disclosure.

[0070] Definitions Unless otherwise specified, the following terms and phrases described herein are intended to have the following meanings.

[0071] When a trade name is used herein, it is intended to independently encompass the trade name product and the active ingredient of the trade name product.

[0072] As used herein, the phrase "compound of formula I" means a compound of formula I or an agriculturally acceptable salt thereof. With respect to isolable intermediates, the phrase "compound of formula (number)" means a compound of that formula and its salts, and optionally, their agriculturally acceptable salts.

[0073] As used herein, the term "alkyl" means a hydrocarbon containing primary, secondary, tertiary, or cyclic carbon atoms. For example, and without limitation, an alkyl group has from 1 to 20 carbon atoms (i.e., C1-C 20It may have 1 to 8 carbon atoms (i.e., C1-C8 alkyl), 1 to 6 carbon atoms (i.e., C1-C6 alkyl), or 1 to 4 carbon atoms (i.e., C1-C4 alkyl). Examples of suitable alkyl groups include methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(CH3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3, and octyl (-(CH2)7CH3), but are not limited thereto.

[0074] As used herein, the term "alkyl" is unsaturated, i.e., carbon-carbon sp 2It means a hydrocarbon containing a primary, secondary, tertiary or cyclic carbon atom at at least one site of a double bond. For example, and without limitation, an alkenyl group has 2 to 20 carbon atoms (i.e., C2-C 20 alkenyl), 2 to 8 carbon atoms (i.e., C2-C8 alkenyl), 2 to 6 carbon atoms (i.e., C2-C6 alkenyl) or 2 to 4 carbon atoms (i.e., C2-C4 alkenyl). Examples of suitable alkenyl groups include, but are not limited to, ethylene or vinyl (-CH=CH2), allyl (-CH2CH=CH2), cyclopentenyl (-C5H7), and 5-hexenyl (-CH2CH2CH2CH2CH=CH2).

[0075] As used herein, the term "alkynyl" means a hydrocarbon containing a primary, secondary, tertiary or cyclic carbon atom having at least one site of an unsaturated, i.e., carbon-carbon, sp triple bond. For example, and without limitation, an alkynyl group has 2 to 20 carbon atoms (i.e., C2-C 20 alkynyl), 2 to 8 carbon atoms (i.e., C2-C8 alkynyl), 2 to 6 carbon atoms (i.e., C2-C6 alkynyl) or 2 to 4 carbon atoms (i.e., C2-C4 alkynyl). Examples of suitable alkynyl groups include, but are not limited to, acetylene (-C≡CH) and propargyl (-CH2C≡CH).

[0076] As used herein, the term "alkoxy" is interchangeable with the term "O(alkyl)", and the "alkyl" group defined above is bonded to the parent molecule through an oxygen atom. For example, and without limitation, the alkyl portion of the O(alkyl) group has 1 to 20 carbon atoms (i.e., C1-C 20It may have 1 to 20 carbon atoms (i.e., C1-C20 alkyl), 1 to 8 carbon atoms (i.e., C1-C8 alkyl), 1 to 6 carbon atoms (i.e., C1-C6 alkyl), or 1 to 4 carbon atoms (i.e., C1-C4 alkyl). Examples of suitable alkoxy or O(alkyl) groups include, but are not limited to, methoxy (-OCH3 or -OMe), ethoxy (-OCH2CH3 or -OEt), and t-butoxy (-O-C(CH3)3 or -OtBu). Similarly, "O(alkenyl)", "O(alkynyl)", and the corresponding substituents will be understood by those skilled in the art.

[0077] As used herein, the term "acyl" is meant to encompass several functional groups such as "C=O(alkyl)", "C=O(alkenyl)", "C=O(alkynyl)", and their corresponding substituents, where the "alkyl", "alkenyl", and "alkynyl" groups are as defined above and are bonded to O, N, S of the parent molecule via the C=O group. For example, and without limitation, the alkyl portion of the C=O(alkyl) group may have 1 to 20 carbon atoms (i.e., C1-C 20 alkyl), 1 to 8 carbon atoms (i.e., C1-C8 alkyl), 1 to 6 carbon atoms (i.e., C1-C6 alkyl), or 1 to 4 carbon atoms (i.e., C1-C4 alkyl). Examples of suitable acyl groups include, but are not limited to, formyl (i.e., carboxaldehyde group), acetyl, trifluoroacetyl, propionyl, and butanoyl. Those skilled in the art will understand that the corresponding definitions apply to the "C=O(alkenyl)" and "C=O(alkynyl)" moieties. In this description, "C=O(alkyl)", "C=O(alkenyl)", "C=O(alkynyl)" are written as "CO(alkyl)", "CO(alkenyl)", and "CO(alkynyl)", respectively.

[0078] As used herein, the term "alkylene" means a saturated, branched or straight-chain or cyclic hydrocarbon radical having two monovalent radical centers derived by removal of two hydrogen atoms from the same or two different carbon atoms of the parent alkane. For example, and without limitation, an alkylene group may have 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Typical alkylene radicals include, but are not limited to, methylene (-CH2-), 1,1-ethyl (-CH(CH3)-), 1,2-ethyl (-CH2CH2-), 1,1-propyl (-CH(CH2CH3)-), 1,2-propyl (-CH2CH(CH3)-), 1,3-propyl (-CH2CH2CH2-), and 1,4-butyl (-CH2CH2CH2CH2-).

[0079] As used herein, the term "alkenylene" means an unsaturated, branched or straight-chain or cyclic hydrocarbon radical having two monovalent radical centers derived by removal of two hydrogen atoms from the same or two different carbon atoms of the parent alkene. For example, and without limitation, an alkenylene group may have 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms or 1 to 4 carbon atoms. Typical alkenylene radicals include, but are not limited to, 1,2-ethylene (-CH=CH-).

[0080] As used herein, the term "alkynylene" means an unsaturated, branched or straight-chain or cyclic hydrocarbon radical having two monovalent radical centers derived by removal of two hydrogen atoms from the same or two different carbon atoms of the parent alkyne. For example, and without limitation, an alkynylene group may have 2 to 20 carbon atoms, 2 to 10 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms. Typical alkynylene radicals include, but are not limited to, acetylene (-C≡C-), propargyl (-CH2C≡C-), and 4-pentynyl (-CH2CH2CH2C≡C-).

[0081] As used herein, the term "aryl" means an aromatic hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of a parent aromatic ring system. For example, and without limitation, an aryl group may have 6 to 20 carbon atoms, 6 to 14 carbon atoms, or 6 to 10 carbon atoms. Typical aryl groups include, but are not limited to, radicals derived from benzene (e.g., phenyl), substituted benzene, naphthalene, anthracene, and biphenyl.

[0082] As used herein, the term "arylalkyl" means an acyclic alkyl radical in which one of the hydrogen atoms bonded to a carbon atom, typically a terminal or sp 3 carbon atom, is replaced by an aryl radical. Typical arylalkyl groups include, but are not limited to, benzyl, 2-phenylethane-1-yl, naphthylmethyl, 2-naphthylethane-1-yl, naphthobenzyl, 2-naphthophenylethane-1-yl, and the like. For example, and without limitation, an arylalkyl group can contain 7 to 20 carbon atoms, for example, the alkyl moiety is 1 to 6 carbon atoms and the aryl moiety is 6 to 14 carbon atoms.

[0083] As used herein, the term "arylalkenyl" means an acyclic alkenyl radical in which one of the hydrogen atoms bonded to a carbon atom, typically a terminal or sp 3 carbon atom, and further an sp 2 carbon atom, is replaced by an aryl radical. The aryl moiety of the arylalkenyl can include, for example, any of the aryl groups described herein, and the alkenyl moiety of the arylalkenyl can include, for example, any of the alkenyl groups described herein. An arylalkenyl group can contain 8 to 20 carbon atoms, for example, the alkenyl moiety is 2 to 6 carbon atoms and the aryl moiety is 6 to 14 carbon atoms.

[0084] As used herein, the term "arylalkynyl" means an acyclic alkynyl radical in which one of the hydrogen atoms attached to a carbon atom, typically a terminal or sp 3 carbon atom, and further an sp carbon atom, is replaced by an aryl radical. The aryl portion of the arylalkynyl can include, for example, any of the aryl groups disclosed herein, and the alkynyl portion of the arylalkynyl can include, for example, any of the alkynyl groups disclosed herein. For example, and without limitation, an arylalkynyl group can contain 8 to 20 carbon atoms, for example, the alkynyl portion has 2 to 6 carbon atoms and the aryl portion has 6 to 14 carbon atoms.

[0085] As used herein, the term "heterocycle" means a group containing a ring closed by a covalent bond in which at least one of the atoms forming the ring is a heteroatom. For example, and without limitation, a heterocyclic ring can be formed by 3, 4, 5, 6, 7, 8, 9, or 9 or more atoms. Any number of these atoms can be heteroatoms (i.e., the heterocyclic ring can contain 1, 2, 3, 4, 5, 6, 7, 8, 9, or more than 9 heteroatoms). In a heterocyclic ring containing two or more heteroatoms, these two or more heteroatoms can be the same as or different from each other. The heterocycle can be substituted. The bond to the heterocycle can be at a heteroatom or through a carbon atom. It should be understood that in this description, the term "heterocycle" also encompasses "heteroaryl" groups.

[0086] As used herein, the term "protecting group" means a moiety of a compound that masks or modifies the properties of a functional group or the properties of the compound as a whole. The chemical substructures of protecting groups can vary widely. One function of a protecting group is to serve as an intermediate in the synthesis of a parent active substance. Chemical protecting groups and strategies for protection / deprotection are well known in the art. See "Protective Groups in Organic Chemistry", Theodora W. Greene (John Wiley & Sons, Inc., New York, 1991).

[0087] As used herein, the term "substituted", when referring to alkyl, alkylene, alkoxy, alkenyl, alkynyl, alkenylene, aryl, alkynylene, etc., e.g., "substituted alkyl", "substituted alkylene", "substituted alkoxy" - or substituted O(alkyl), "substituted alkenyl", "substituted alkynyl", "substituted alkenylene", "substituted aryl" and "substituted alkynylene", each means alkyl, alkylene, alkoxy, alkenyl, alkynyl, alkenylene, aryl and alkynylene, respectively, wherein one or more hydrogen atoms are each independently replaced by a non-hydrogen substituent, unless otherwise indicated.

[0088] Typical non-hydrogen substituents are -X, -R B , -O - , =O, -OR B , -SR B , -S - , -NR B 2, Si(R C )3, -N + R B 3, -NR b -(Alk)-NR B 2, -NR B -(Alk)-N + R B 3, -NR B -(Alk)-OR B , -NR B -(Alk)-OP(=O)(OR B )(O - ), -NRB -(Alk)-OP(=O)(OR B )2, -NR B -(Alk)-Si(R C )3, -NR B -(Alk)-SR B 、-O-(Alk)-NR B 2, -O-(Alk)-N + R B 3, -O-(Alk)-OR B 、-O-(Alk)-OP(=O)(OR B )(O - )、_-O-(Alk)-OP(=O)(OR B )2, -O-(Alk)-Si(R C )3, -O-(Alk)-SR B 、=NR B 、-CX3, -CN, -OCN, -SCN, -N=C=O, -NCS, -NO, -NO2, =N2, -N3, -NHC(=O)R B 、-OC(=O)R B 、-NHC(=O)NR B 2, -S(=O)2-, -S(=O)2OH, -S(=O)2R B 、-OS(=O)2OR B 、-S(=O)2NR B 2, -S(=O)R B 、-OP(=O)(OR B (O - )、-OP(=O)(OR B )2, -P(=O)(OR B )2, -P(=O)(O - )2, -P(=O)(OH)2, -P(O)(OR B (O - )、-C(=O)R B 、-C(=O)X, -C(S)R B 、-C(O)OR B 、-C(O)O - 、-C(S)OR B 、-C(O)SR B 、-C(S)SR B 、-C(O)NR B 2, -C(S)NR B 2 or -C(=NR B )NR Bincluding, but not limited to, 2, wherein each X is independently a halogen: F, Cl, Br, or I, and each R B is independently H, alkyl, aryl, arylalkyl, heterocycle, an alkyloxy group such as poly(ethyleneoxy), PEG or poly(methyleneoxy), or a protecting group, and each R C is independently alkyl, O(alkyl) or O(tri-substituted silyl), and each Alk is independently alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene or substituted alkynylene. Unless otherwise specified, when the term "substituted" is used in combination with a group such as arylalkyl having two or more substitutable moieties, the substituent can be bonded to the aryl moiety, the alkyl moiety, or both.

[0089] It should also be understood that the term "tri-substituted silyl" refers to a silyl group independently substituted with three functional groups selected from alkyl, alkenyl, alkynyl, aryl and arylalkyl. Non-limiting examples of tri-substituted silyl groups include trimethylsilyl and dimethylphenylsilyl.

[0090] As used herein, the term "PEG" or "poly(ethylene glycol)" is meant to encompass any water-soluble poly(ethylene oxide). Typically, substantially all or all of the monomer subunits are ethylene oxide subunits, but PEG may contain distinct end-capping moieties or functional groups. Depending on whether the terminal oxygen is displaced, the PEG chains described herein have the following structures, -(CH2CH2O) m - or -(CH2CH2O) m-1It can contain one of CH2CH2-, wherein m is an integer optionally selected from 1 to 100, 1 to 50, 1 to 30, 5 to 30, 5 to 20, or 5 to 15. PEG can be capped with an "end-capping group" which is generally an inert carbon-containing group bonded to the terminal oxygen or other terminal atom of PEG. Non-limiting examples of end-capping groups can include alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, CO(alkyl), CO(substituted alkyl), CO(alkenyl), CO(substituted alkenyl), CO(alkynyl) or CO(substituted alkynyl).

[0091] One of ordinary skill in the art will recognize that the substituents and other moieties of the compounds described herein should be selected to provide agriculturally useful compounds that can be formulated in an agriculturally acceptable and stable composition that can be applied to plants. Definitions and substituents for the various genera and subgenera of the compounds described herein are set forth and exemplified in this description. It should be understood by one of ordinary skill in the art that no combination of the definitions and substituents described herein should result in inoperable species or compounds. The phrase "inoperable species or compounds" is also understood to mean a compound structure that violates the relevant scientific principles (e.g., a carbon atom connected to more than four covalent bonds, etc.) or a compound that is too unstable to be isolated and formulated into an agriculturally acceptable composition.

[0092] Selected substituents of the compounds described herein can be present to a recursive extent. In this context, a "recursive substituent" means that the substituent can enumerate another example of itself. Due to the recursive nature of such substituents, theoretically, a large number of compounds can exist in any given implementation. For example, R x contains the R y substituent. R y can be R, R can be W 3 and can be. W 3 can be W 4 and can be, W 4 can be R, or R yIt can contain substituents including. Those skilled in the art of organic chemistry will understand that the total number of such substituents will be reasonably limited by the desired properties of the intended compound. Such properties include, by way of example and without limitation, physical properties such as molecular weight, solubility or log P, application properties such as activity against the intended target, the possibility of application to plants, and practical properties such as ease of synthesis. Typically, each recursive substituent can occur independently 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0 times in a given implementation. For example, each recursive substituent can occur independently 3 times or less in a given embodiment. Recursive substituents are an intended aspect of the compounds described herein. Those skilled in the art of organic chemistry understand the versatility of such substituents.

[0093] As used herein, the term "agriculturally acceptable salt" refers to a salt that exhibits pesticidal activity (i.e., is active against one or more biotic stresses) or can improve the resistance of plants to one or more abiotic stresses. This term also refers to a salt that is converted or can be converted to a compound or salt that exhibits pesticidal activity or can improve the resistance of plants to one or more abiotic stresses in plants, water, or soil. "Agriculturally acceptable salts" can be agriculturally acceptable cations or agriculturally acceptable anions. Non-limiting examples of agriculturally acceptable cations can include cations derived from alkali or alkaline earth metals, as well as cations derived from ammonia and amines. For example, agriculturally acceptable cations can include sodium, potassium, magnesium, alkylammonium, and ammonium cations. Non-limiting examples of agriculturally acceptable anions can include halides, phosphates, alkyl sulfates, and carboxylate anions. For example, agriculturally acceptable anions can include chloride, bromide, methyl sulfate, ethyl sulfate, acetate, lactate, dimethyl phosphate, or polyalkoxylated phosphate anions.

[0094] As used herein when referring to a particular moiety of the compounds described herein, the term "optionally substituted" means that all substituents are hydrogen or that one or more of the hydrogens of the moiety can be replaced by substituents such as those listed under the definition of "substituted" or otherwise indicated.

[0095] All enantiomers, diastereomers, and racemic mixtures, tautomers, polymorphs, and pseudopolymorphs of the compounds within the scope of the formulas and compositions described herein, as well as their agriculturally acceptable salts, are understood to be encompassed by this description. All mixtures of such enantiomers and diastereomers are also within the scope of this description.

[0096] The compounds described herein and their agriculturally acceptable salts can exist as different polymorphs or pseudopolymorphs. As used herein, crystal polymorphism means the ability of a crystalline compound to exist in different crystal structures. Crystal polymorphism can be due to differences in crystal packing (packing polymorphism) or differences in packing between different conformational isomers of the same molecule (conformational polymorphism). As used herein, crystal pseudopolymorphism means the ability of hydrates or solvates of a compound to exist in different crystal structures. The pseudopolymorphs of the compounds described herein can exist due to differences in crystal packing (packing pseudopolymorphism) or differences in packing between different conformational isomers of the same molecule (conformational pseudopolymorphism). The description and depiction of the compounds described herein are intended to include all polymorphs and pseudopolymorphs of the compounds and their agriculturally acceptable salts.

[0097] The compounds described herein and their agriculturally acceptable salts can also exist as amorphous solids. As used herein, an amorphous solid is a solid in which there is no long-range order in the positions of the atoms. The description and depiction of the compounds described herein are intended to include all amorphous forms of the compounds and their agriculturally acceptable salts.

[0098] The modifier "about" as used in connection with a quantity includes the recited value and has the meaning ascribed to it by the context. For example, the modifier "about" can include the degree of error associated with the measurement of a quantity.

[0099] For agricultural use (i.e., application to plants), salts of the compounds described herein are agriculturally acceptable salts. However, salts that are not agriculturally acceptable can also find use, for example, in the preparation or purification of agriculturally acceptable compounds. Accordingly, all salts, whether or not they are agriculturally acceptable salts, are to be understood as being within the scope described herein.

[0100] It will be understood that the compounds described herein can exist in their non-ionized, ionized, and zwitterionic forms and can be combined with various amounts of water (e.g., stoichiometric amounts of water) such as hydrates.

[0101] Whenever the compounds described herein are substituted with two or more of the same named groups, e.g., "R 1 " or "R 2 ", it will be understood that the groups can be the same or different, i.e., each group is independently selected. For example, in the expression "Si(OR 7 )3 where each R 7 is independently alkyl or aryl", it will be understood that each R 7 can be independently selected from alkyl groups and aryl groups. Accordingly, Si(OR 7 )3 includes both asymmetric groups where all three R 7 are the same, at least one R 7 group is different from the other two R 7 groups, or each R 7 group is different. This is also understood to apply to all R q or Z q groups defined herein (e.g., q is selected from 1 - 17, a - f or A - C). The group "Z 1 " is "Z 1 =Z2 Only when it is explicitly stated that it is "Z 2 ", will it be necessarily understood to be the same as "Z".

[0102] The compounds described herein may also exist in certain cases as tautomeric forms. Only one delocalized resonance structure is typically depicted, but all such forms are contemplated within the scope of this description. For example, various tautomers may exist for the tetrapyrrole ring systems described herein, and all their possible tautomers are within the scope of this description.

[0103] As used herein, the term "growth medium" refers to any soil (of any composition) or soilless (e.g., hydroponic) medium suitable for the growth and cultivation of plants. The growth medium can further comprise any naturally occurring and / or synthetic substances suitable for the growth and cultivation of plants. As used herein, the phrase "any surface of the growth medium" or "surface of the growth medium" refers to a surface directly exposed to natural light and / or simulated light and / or weather.

[0104] As used in this description, the term "applying" refers to contacting at least one combination or composition of the present disclosure with the surface of a plant or the surface of a growth medium, or an area beneath the surface of the growth medium (e.g., by soil injection), or any combination thereof, or contacting at least one combination or composition of the present disclosure directly with a plant (e.g., by spraying), by any means known in the art (e.g., injection, root bathing, soil perfusion, drip irrigation, etc.).

[0105] As used herein, the term "crop plant" refers to non-woody plants that grow in a cycle of one year or less as a source of food and / or energy, tend to be harvested, and are harvested. Non-limiting examples of crop plants include sugarcane, wheat, rice, corn (maize), potato, sugar beet, barley, sweet potato, cassava, soybean, tomato, and leguminous plants (beans and peas).

[0106] As used herein, the term "woody plant" refers to woody perennial plants (e.g., trees) that have a single stem or trunk and have lateral branches at a certain distance from the ground. Woody plants can be deciduous trees, evergreen trees (e.g., conifers) or shrubs. Non-limiting examples of woody plants include maple trees, citrus trees, apple trees, pear trees, oak trees, paulownia trees, pine trees, and fir trees.

[0107] As used herein, the term "turfgrass" refers to cultivated grasses of the Poaceae family that provide ground cover, e.g., turf or lawns that are regularly cut or mowed to maintain a certain height. Grasses of the Poaceae family belong to the Poaceae family and are subdivided into six subfamilies, three of which include the following common turfgrasses, the Festucoideae subfamily of cool-season turfgrasses, and the Panicoideae and Eragrostoideae subfamilies of warm-season turfgrasses. A limited number of species are in wide use as turfgrasses and generally meet the criteria of forming a relatively uniform soil cover and being tolerant of mowing and traffic. Generally, turfgrasses have a compressed crown that facilitates mowing without cutting the growing point. In this context, the term "turfgrass" includes areas where one or more grass species of the Poaceae family are cultivated to form a relatively uniform soil cover, blends that are combinations of different cultivars of the same species, or mixtures that are combinations of different species and / or cultivars.

[0108] Non-limiting examples of grasses include bluegrasses (e.g., Kentucky bluegrass), bentgrasses (e.g., creeping bentgrass), redtop, fescues (e.g., red fescue), ryegrasses (e.g., annual ryegrass), wheatgrasses (e.g., crested wheatgrass), beachgrasses, brome grasses (e.g., Arizona brome), cattails (e.g., sand cattail), alkaligrass (Puccinellia distans), crested dog's-tail (Cynosurus cristatus), bermudagrass (Cynodon spp. such as Cynodon dactylon), hybrid bermudagrass (e.g., tifdwarf bermudagrass), zoysiagrasses (e.g., Zoysia japonica), St. Augustinegrass (e.g., Bitter Blue St. Augustinegrass), centipedegrass (Eremochloa ophiuroides), carpetgrass (Axonopus fissifolius), bahiagrass (Paspalum notatum), kikuyugrass (Pennisetum clandestinum), buffalograss (Buchloe dactyloids), seashore paspalum (Paspalum vaginatum), blue grama (Bouteloua gracilis), black grama (Bouteloua eriopoda), sideoats grama (Bouteloua curtipendula), Sporobolusspp. (e.g., Alkali Sacaton), Sand Dropseed (Sporobolus cryptandrus), Prairie Dropseed (Sporobolus heterolepis), Hordeum spp. (e.g., California Barley), common barley, Meadow Barley, Alopecurus spp. (e.g., Creeping Foxtail and Meadow Foxtail), Stipa spp. (e.g., Needle & Thread), Elymus spp. (e.g., Blue Wildrye), Buffelgrass (Cenchrus ciliaris), Big Quaking Grass (Briza maxima), Big Bluestem (Andropogon gerardii), Little Bluestem (Schizachyruim scoparium, Sand Bluestem (Andropogon hallii), Deergrass (Muhlenbergia rigens), Eastern Gamagrass (Tripsacum dactyloides), Galleta (Hilaria jamesii), Tufted Hairgrass (Deschampsia caespitosa), Indian Rice Grass (Oryzopsis hymenoides), Indian Grass (Sorghastrum nutans), Sand Lovegrass (Eragrostis trichodes), Weeping Lovegrass (Eragrostis curvula), California Melic (Melicainclude California brome (Bromus carinatus), Prairie Junegrass (Koeleria pyramidata), Prairie Sandreed (Calamovilfa longifolia), Redtop (Agrostis alba), Reed Canarygrass (Phalaris arundinacea), Sloughgrass (Spartina pectinata), Green Sprangletop (Leptochloa dubia), Bottlebush Squirreltail (Sitanion hystrix), Switchgrass (Panicum virgatum), and Purple Threeawn (Aristida purpurea).

[0109] As used herein, the phrase "promoting plant health" includes at least one of controlling diseases, conditions, or injuries caused by plant pests and increasing abiotic stress resistance or tolerance in plants. In other words, the phrase "promoting plant health" includes at least one of "controlling plant infection by one or more biological agents", "controlling plant infestation by one or more insects", and "increasing plant resistance to one or more abiotic stresses".

[0110] As used herein, the phrase "controlling plant infection by a biological agent" means reducing, alleviating, or stabilizing an infection and / or other existing undesirable conditions or side effects caused by the association of a microbial pathogen with a plant or infestation of an insect. Microbial pathogens can include fungi, bacteria (gram positive or gram negative), viruses, viroids, virus-like organisms, phytoplasmas, and the like.

[0111] As used herein, the term "abiotic stress" refers to environmental conditions that adversely affect crop and other plant growth, development, yield, and yield quality below optimal levels. Non-limiting examples of abiotic stress include, for example, photooxidative conditions, drought (water deficit), excessive watering (flooding, and waterlogging), extreme temperatures (cold, freezing and heat), extreme levels of light (intense and weak), radiation (UV-B and UV-A), excessive Na + (sodium) salts, chemical factors (e.g., pH), mineral (metal and metalloid) toxicity, deficiency or excess of essential nutrients, gaseous pollutants (ozone, sulfur dioxide), wind, mechanical factors, and other stress factors.

[0112] As used herein, the term "increasing stress resistance" (etc.) refers to an increase in the ability of a plant to survive or thrive in a stress condition. Enhanced resistance or tolerance can be specific to a particular stress factor, e.g., drought, excess water, nutrient deficiency, salt, cold, shade or heat, or multiple stress factors. In some scenarios, increased resistance to one or more abiotic stresses can be exemplified by a reduction in the decline of plant quality compared to untreated plants exposed to the same stress. In other scenarios, increased resistance to one or more abiotic stresses can be exemplified by maintained or improved plant quality compared to untreated plants exposed to the same stress.

[0113] Photosensitizer compound The compositions described herein can enable the photodynamic inhibition of biological agents (i.e., microbial pathogens and / or insects) that may be present on plants and / or protect plants from abiotic stress, and contain a photosensitizer compound. The photosensitizer compound reacts to light by generating reactive oxygen species (ROS).

[0114] Depending on the type of ROS generated, photosensitizers can be classified into two classes, namely type I photosensitizers and type II photosensitizers. On the one hand, when type I photosensitizers are excited at an appropriate wavelength in the presence of oxygen, short-lived free radicals are formed through electron abstraction or transfer from the substrate. On the other hand, type II photosensitizers form a highly reactive oxygen state known as "singlet oxygen", which is also referred to herein as "reactive singlet oxygen species". Singlet oxygen is generally relatively long-lived and can have a large radius of action.

[0115] It should be understood that the photosensitizer compound can be metallized or non-metallized. When metallized, the metal can be selected to produce either a type I or type II photosensitizer in response to light exposure, as can be the case for various nitrogen-containing macrocyclic compounds that complex with the metal. For example, when a chlorin-type compound is metallized with copper, the ROS generated is typically a type I photosensitizer. When the same chlorin-type compound is metallized with magnesium, the ROS generated is typically a type II photosensitizer. Both type I and type II photosensitizers can be used to enable the photodynamic inhibition of biological mediators present in plants or to protect plants from abiotic stress. In some scenarios, the photosensitizer compound is a type I photosensitizer. In other scenarios, the photosensitizer compound is a type II photosensitizer.

[0116] It should be understood that the term "singlet oxygen photosensitizer" as used herein refers to a compound that produces reactive singlet oxygen species when excited by light. In other words, the term "singlet oxygen photosensitizer" refers to a photosensitizer in which the type II process defined above is dominant compared to the type I process.

[0117] In some embodiments, the photosensitizer compound can be a photosensitizing nitrogen-containing macrocyclic compound comprising four nitrogen-containing heterocyclic rings bonded to each other. In some embodiments, the nitrogen-containing heterocyclic rings are selected from the group consisting of pyrrole and pyrroline and are linked together by methine groups (i.e., =CH- groups) to form a tetrapyrrole. The nitrogen-containing macrocyclic compound can be, for example, a porphyrin compound (e.g., four pyrrole groups linked together by methine groups), a chlorin compound (three pyrrole groups and one pyrroline group linked together by methine groups), a bacteriochlorin compound or an isobacteriochlorin compound (two pyrrole groups and two pyrroline groups linked together by methine groups), or a porphyrinoid (such as texaphrin or subporphyrin), or a functional equivalent thereof having a heterocyclic aromatic ring core or a partially aromatic ring core (i.e., a ring core that is not aromatic throughout its entire circumference), or again a multi-pyrrole compound (such as boron-dipyrromethene). It should be understood that the term "nitrogen-containing macrocyclic compound" can be one of the compounds listed herein or a combination of the compounds listed herein. Thus, the nitrogen-containing macrocyclic compound can include porphyrin, reduced porphyrin, or a mixture thereof. Such nitrogen-containing macrocyclic compounds can also be referred to as "multi-pyrrole macrocyclic compounds" (e.g., tetrapyrrole macrocyclic compounds).

[0118] It should be understood that the term "reduced porphyrin" as used herein refers to the group consisting of chlorin, bacteriochlorin, isobacteriochlorin, and other types of reduced porphyrins such as corrin and corphin.

[0119] It should be understood that the nitrogen-containing macrocyclic compound can be a non-metallic macrocycle (e.g., chlorin e6, protoporphyrin IX or tetraphenylporphyrin) or a metal macrocyclic complex (e.g., Mg-porphyrin, Mg-chlorophyllin, Cu-chlorophyllin, Fe-protoporphyrin IX, etc.). The nitrogen-containing macrocyclic compound can be an extracted naturally occurring compound or a synthetic compound.

[0120] In an implementation form where a porphyrin or reduced porphyrin compound is metallized, the metal can be selected such that the metallized nitrogen-containing macrocyclic compound is a type I photosensitizer or a type II photosensitizer that generates singlet oxygen species. For example, in the case of chlorin and porphyrin, non-limiting examples of metals that generally enable the generation of singlet oxygen species through the formation of type II photosensitizers are Mg, Zn, Pd, Sn, Al, Pt, Si, Ge, Ga, and In. Similarly, non-limiting examples of metals known to form type I photosensitizers when complexed with chlorin and / or porphyrin are Cu, Co, Fe, Ni, and Mn.

[0121] It should be understood that when a metal species is mentioned without its oxidation degree, all suitable oxidation states of the metal species will be considered as understood by those skilled in the art. In other implementation forms, the metal species can be selected from the group consisting of Mg(II), Zn(II), Pd(II), Sn(IV), Al(III), Pt(II), Si(IV), Ge(IV), Ga(III), and In(III). In still other implementation forms, the metal species can be selected from the group consisting of Cu(II), Co(II), Fe(II), and Mn(II). In still other implementation forms, the metal species can be selected from the group consisting of Co(III), Fe(III), Fe(IV), and Mn(III).

[0122] It should also be understood that the specific metals that may lead to the formation of type II photosensitizers and the metals that may lead to the formation of type I photosensitizers can vary depending on the type of nitrogen-containing macrocyclic compound to which they are bound. It should also be understood that non-metallated nitrogen-containing macrocyclic compounds can be either type I photosensitizers or type II photosensitizers. For example, chlorin e6 and protoporphyrin IX are both type II photosensitizers.

[0123] It should be understood that the nitrogen-containing macrocyclic compounds used in the methods and compositions described herein can also be selected based on their toxicity to humans or based on their impact on the environment. For example, porphyrins and reduced porphyrins tend to have lower toxicity to humans and similarly enhanced environmental biodegradation properties when compared to other types of nitrogen-containing macrocyclic compounds such as phthalocyanines.

[0124] The following formulas illustrate some non-limiting examples of nitrogen-containing macrocyclic compounds that can be used in the methods and compositions described herein.

Chemical formula

[0125] Various nitrogen-containing macrocyclic compounds such as Zn-TPP and Mg-chlorophyllin may be obtained from chemical suppliers such as Organic Herb Inc., Sigma Aldrich, or Frontier Scientific. In some scenarios, the nitrogen-containing macrocyclic compound is not 100% pure and may contain other components such as organic acids and carotenoids. In other scenarios, the nitrogen-containing macrocyclic compound may have a high level of purity.

[0126] Modified Ce6 photosensitizer One of the above compounds, Chlorin e6 (Ce6), is a tetrapyrrole having a macrocyclic ring of 20 carbon atoms, with each pyrrole linked to two other pyrroles of the macrocyclic ring by a one-carbon bridge. In the following depiction of Ce6, the carbons of the macrocyclic ring are numbered 1 to 20. In the chemical structure of Ce6, three carboxylic acid-containing groups are provided at the positions of C13(COOH), C15(CH2COOH), and C17(CH2CH2COOH).

Chem.

[0127] The photosensitizer compounds described herein may be based on the above Ce6 scaffold in which at least one of the C13, C15 and C17 carboxylic acids may be functionalized. The modified Ce6 compounds may be metallated or non-metallated. Examples of such modified Ce6, their activities and methods of manufacture are described in PCT Patent Application No. PCT / CA2020 / 050083, which is hereby incorporated by reference in its entirety.

[0128] In some embodiments, the modified Ce6 is a compound of formula I,

Chem.

Chemical formula

Chemical formula

[0129] In some embodiments, the modified Ce6 is a compound of formula I,

Chemical formula

Chemical formula

Chemical formula

[0130] In some embodiments, the modified Ce6 is a compound of formula I,

Chemical formula

Chemical formula

Chemical formula

[0131] In some embodiments,

Chemical formula

Chemical formula

[0132]

Chemical formula

[0133] In some embodiments, each R a 、Rb , R c , R d , R e and R f are, independently, alkyl or alkenyl. For example, and without limitation, R a , R c , R e and R f can be methyl, R b can be vinyl, R d can be ethyl.

[0134] In some embodiments, M is 2H. In some embodiments, M is a metal species selected from the group consisting of Mg, Zn, Pd, Sn, Al, Pt, Si, Ge, Ga, In, Cu, Co, Fe and Mn. It is to be understood that when a metal species is referred to without its degree of oxidation, all suitable oxidation states of the metal species will be considered as would be understood by one of ordinary skill in the art. In other embodiments, M is a metal species selected from the group consisting of Mg(II), Zn(II), Pd(II), Sn(IV), Al(III), Pt(II), Si(IV), Ge(IV), Ga(III) and In(III). In still other embodiments, M is a metal species selected from the group consisting of Cu(II), Co(II), Fe(II) and Mn(II).

[0135] In some embodiments, each R 1 , R 2 , R 4 , R 6 , R 8 , R 9 , R 10 , R 11 and R 12 is, independently, H, alkyl or substituted alkyl. In some embodiments, each R 3 and R 5 is, independently, alkyl or substituted alkyl. In some embodiments, R 13 is H, alkyl, substituted alkyl, CO(alkyl) or CO(substituted alkyl).

[0136] In some embodiments, the compound is selected such that at least one of the following is true: R 1 is H, and R 2 is H, and R 3 is alkyl, and R 4 is H or alkyl, and R 5 is alkyl, and R 6 is alkyl, and R 7 is O(trisubstituted silyl), and R 8 is -(CH2) q -(CH2CH2O) m -R 13 and R 9 is alkyl, and R 10 is alkyl, and R 11 is alkyl, and R 12 is H, and R 13 is H, alkyl, alkenyl, CO(alkyl) or CO(alkenyl).

[0137] In some embodiments, W + is selected from the group consisting of sodium, potassium, magnesium and ammonium cations. In some embodiments, Y - is selected from the group consisting of chloride, bromide, phosphate, dimethyl phosphate, methyl sulfate, ethyl sulfate, acetate and lactate.

[0138] In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. Similarly, in some embodiments, p is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. With respect to the PEG portion, m can be an integer selected from 1 to 100, or 1 to 80, or 1 to 60, or 1 to 50, or 1 to 30, or 1 to 20, or 1 to 10, or 5 to 30, or 5 to 20, or 5 to 10. Similarly, in some embodiments, q is an integer selected from 0 to 16, or 0 to 12, or 0 to 8, or 0 to 6, or 0 to 4. In some embodiments, q = 1. In yet other embodiments, q = 0.

[0139] In some embodiments, Z 2 is NR 2 R 3 、NR 2 -(CH2) n -NR 4 R 5 、NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - 、NR 2 -(CH2) n -O(PO3H) - W + 、NR 2 -(CH2) n -Si(R 7 )3、NR 2 -(CH2) n -SR 8 、 NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9R 10 R 11 Y - and NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + and NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R 7 )3, and NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 and OR 3 and O(CH2) n -NR 4 R 5 and O(CH2) n -N + R 4 R 5 R 6 Y - and O(CH2) n -O(PO3H) - W + and O(CH2) n -Si(R 7 )3, and O(CH2) n -SR 8 、 O(CH2) n -NR 4 -(CH2) p -NR 9 R 10 and O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - and O(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7) 3, and Z 3 is OR 12 or Z 3 = Z 2 is the case.

[0140] In some embodiments, Z 2 is NR 2 R 3 , NR 2 -(CH2) n -NR 4 R 5 , NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - , NR 2 -(CH2) n -O(PO3H) - W + , NR 2 -(CH2) n -Si(R 7 )3, NR 2 -(CH2) n -SR 8 , NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 and Z 3 is OR 12 or Z 3 = Z 2 is the case.

[0141] In some embodiments, Z 3 is OR 12 For example, Z 3 can be OH. In other embodiments, Z 3 = Z 2 is the case.

[0142] In some embodiments, the modified Ce6 is a compound of formula I-B1,

Chemical Formula

[0143] In some embodiments, R 1 is H, R 2 is H, and / or R 3 is alkyl. R 3 can be, for example, (C1-C 12 ) alkyl, (C1-C8) alkyl or (C1-C4) alkyl. In some embodiments, Z 3 is OR 12 and R 12 can be H. In other embodiments, Z 3 =NR 2 R 3 is.

[0144] In some embodiments, the modified Ce6 is a compound of formula I-B2, [Chemical formula] or an agriculturally acceptable salt thereof, wherein Z 1 is OR 1 and R 5 is alkyl, substituted alkyl, or -(CH2) p -NR 9 R 10 and each R 2 , R 4 , R 9 and R 10 are independently H, alkyl or substituted alkyl, n is an integer selected from 1 to 16, p is an integer selected from 1 to 16, Z 3 is OR 12 or Z 3 =NR 2 -(CH2) n -NR 4 R 5 and each R 1 and R 12 are independently H, alkyl or substituted alkyl, each R a , R b , R c , R d , R e and R f are independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl, M is 2H or a metal species, Substituted alkyl, substituted alkenyl and substituted alkynyl groups are independently substituted with one or more of F, Cl, Br, I, hydroxy, CN and N3.

[0145] In some embodiments, R 1 is H, R 2 is H, and / or R 4is H or alkyl. In some embodiments, R 4 is H, and R 5 is alkyl. In some embodiments, R 4 and R 5 are alkyl. R 4 and / or R 5 can be, for example, (C1-C 12 )alkyl, (C1-C8)alkyl or (C1-C4)alkyl. In some embodiments, R 5 is -(CH2) p -NR 9 R 10 . In some embodiments, R 9 and R 10 are alkyl, or R 9 is H and R 10 is alkyl. R 9 and / or R 10 can be, for example, (C1-C 12 )alkyl, (C1-C8)alkyl or (C1-C4)alkyl. In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4.

[0146] In some embodiments, the modified Ce6 is a compound of formula I-B3,

Chemical formula

[0147] In some embodiments, R 1 is H, R 2 is H, and / or R 12 is H or alkyl. In some embodiments, R 7 is alkyl, O(alkyl) or O(trisubstituted silyl), and the alkyl group is (C1-C 12 )alkyl, (C1-C8)alkyl or (C1-C4)alkyl. In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. In some embodiments, Z3 is OR 12 In other embodiments, Z 3 = NR 2 -(CH2) n -Z 4 is

[0148] In some embodiments, the modified Ce6 is a compound of formula I-B4a,

Chemical formula

[0149] In some embodiments, R 1 is H, R 2 is H, and / or R12 is H or alkyl. In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. W + is selected from the group consisting of sodium, potassium, magnesium and ammonium cations. In some embodiments, Z 3 is OR 12 In other embodiments, Z 3 =NR2-(CH2) n -O(PO3H) - W + In some embodiments, the modified Ce6 is a compound of formula I-B4c,

[0150] or an agriculturally acceptable salt thereof,

Chemical formula

[0151] In some embodiments, R 1 is H, R 2 is H, and / or R 12 is H or alkyl. In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. In some embodiments, R 4 , R 5 and R 6 are alkyl, and optionally R 4 =R 5 =R 6 is. Y - is selected from the group consisting of chloride, bromide, phosphate, dimethyl phosphate, methyl sulfate, ethyl sulfate, acetate and lactate. In some embodiments, Z 3 is OR 12 . In other embodiments, Z 3 =NR2-(CH2) n -NR 4 R 5 R 6+ Y - is.

[0152] In some embodiments, the modified Ce6 is a compound of Formula I-C,

Chemical formula

Chemical formula

Chemical formula

[0153] In some embodiments, R 1 is H and / or R 12 is H. In some embodiments, m is an integer selected from 5 to 100, or 5 to 80, or 5 to 50, or 5 to 20, or 5 to 10. In some embodiments, Z 3 is OR 12 . In other embodiments, Z 3=O(CH2CH2O) m -R 13 wherein, in some embodiments, R 13 is H, alkyl, alkenyl, CO(alkyl) or CO(alkenyl).

[0154] Non-limiting examples of modified Ce6 photosensitizers include the following:

Chem.

Chem.

Chem.

Chem.

[0155] Modified PP IX photosensitizer One of the above compounds, protoporphyrin IX (PP IX), is one of the most common porphyrins in nature. PP IX is a dark-colored pigment found naturally in the form of its iron complex. When complexed with ferrous iron, the molecule is called heme. Other iron complexes have also been synthesized using, for example, Fe(III) or Fe(IV). PP IX is a mostly planar tetrapyrrole having a macrocyclic ring of 20 carbon atoms, with each pyrrole linked to two other pyrroles of the macrocyclic ring by a one-carbon bridge. In the following depiction of PP IX, the carbon atoms of the macrocyclic ring are numbered 1 - 20. In the chemical structure of PP IX, two carboxylic acid-containing moieties are provided at the positions of C13(CH2CH2COOH) and C17(CH2CH2COOH).

Chem.

[0156] The photosensitizer compounds described herein may be based on a PP IX scaffold in which at least one of the C13 and C17 carboxylic acids may be functionalized. The modified PP IX compounds may be metallated or non-metallated. Examples of such modified PP IX, their activities and methods of manufacture are described in PCT Patent Application No. PCT / CA2020 / 050197, which is hereby incorporated by reference in its entirety.

[0157] In some embodiments, the modified PP IX is a compound of formula II,

Chemical formula

[0158] In some embodiments, the compound of Formula II is: Z 1 and Z 2 one of which is OR 1 and Z 1 and Z 2 the other of which is NR 2 R 3 NR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - NR 2 -(CH2) n -O(PO3H) - W + NR 2 -(CH2) n -Si(R 7 )3, NR 2 -(CH2) n -SR 8 、 NR 2 -(CH2) n -NR4 -(CH2) p -NR 9 R 10 、NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + 、NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R 7 )3、NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 、O(CH2) n -NR 4 R 5 、O(CH2) n -N + R 4 R 5 R 6 Y - 、O(CH2) n -O(PO3H) - W + 、O(CH2) n -Si(R 7 )3、O(CH2) n -SR 8 、 O(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、O(CH2) n -NR4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3, or Z 1 is NR 2 R 3 、NR 2 -(CH2) n -NR 4 R 5 、NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - 、NR 2 -(CH2) n -O(PO3H) - W + 、NR 2 -(CH2) n -Si(R 7 )3、NR 2 -(CH2) n -SR 8 、 NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + 、NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R7 )3, NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 , O(CH2) n -NR 4 R 5 , O(CH2) n -N + R 4 R 5 R 6 Y - , O(CH2) n -O(PO3H) - W + , O(CH2) n -Si(R 7 )3, O(CH2) n -SR 8 、 O(CH2) n -NR 4 -(CH2) p -NR 9 R 10 , O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - , O(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3, Z 2 =Z 1 and Each R 1 and R 2 are independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, or substituted alkynyl; R 3is alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl, each R 4 、R 6 、R 8 、R 9 、R 10 and R 11 is independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl or -(CH2) q -(CH2CH2O) m -R 13 wherein, R 5 is alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, or -(CH2) q -(CH2CH2O) m -R 13 wherein, R 7 is alkyl, O(alkyl) or O(trisubstituted silyl), R 13 is H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, CO(alkyl), CO(substituted alkyl), CO(alkenyl), CO(substituted alkenyl), CO(alkynyl) or CO(substituted alkynyl), W + is an agriculturally acceptable cation, Y - is an agriculturally acceptable anion, n is an integer selected from 1 to 16, p is an integer selected from 1 to 16, m is an integer selected from 1 to 100, q is an integer selected from 0 to 16, each R a 、R b 、R c 、R d 、R e and R fis independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl,

Chemical formula

Chemical formula

[0159] In some implementations, Z 1 =Z 2 =NR 2 R 3 is. In other implementations, Z 1 is NR 2 R 3 and Z 2 is OH, or Z 1 is OH and Z 2 is NR 2 R 3 is. R 3 can be, for example, alkyl or substituted alkyl.

[0160] In some implementations,

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0161] In some implementations, each R a , R b , R c , R d , R e and R f is, independently, alkyl or alkenyl. In non - limiting examples, R a , R c , R e and R f are methyl, while on the other hand, R b and R d are vinyl.

[0162] In some embodiments, M is 2H. In some embodiments, M is a metal species selected from the group consisting of Mg, Zn, Pd, Sn, Al, Pt, Si, Ge, Ga, In, Cu, Co, Fe, and Mn. It should be understood that when a metal species is referred to without its degree of oxidation, all suitable oxidation states of the metal species will be considered as understood by those skilled in the art. In other embodiments, M is a metal species selected from the group consisting of Mg(II), Zn(II), Pd(II), Sn(IV), Al(III), Pt(II), Si(IV), Ge(IV), Ga(III), and In(III). In yet other embodiments, M is a metal species selected from the group consisting of Cu(II), Co(II), Fe(II), and Mn(II). In still other embodiments, M is a metal species selected from the group consisting of Cu(II), Co(III), Fe(III), and Mn(III).

[0163] In some embodiments, each R 1 , R 2 , R 4 , R 6 , R 8 , R 9 , R 10 , and R 11 is independently H, alkyl, or substituted alkyl. In some embodiments, each R 3 and R 5 is independently alkyl or substituted alkyl. In some embodiments, R 13 is H, alkyl, substituted alkyl, CO(alkyl), or CO(substituted alkyl).

[0164] In some embodiments, the compound of Formula II is selected such that at least one of the following is true: R 1 is H, R 2 is H, R 3 is alkyl, R 4 is H or alkyl, R 5 is alkyl, R 6 is alkyl, R 7 is O(trisubstituted silyl), R8 is H or alkyl, R 9 is alkyl, R 10 is alkyl, R 11 is alkyl, R 13 is H, alkyl, alkenyl, CO(alkyl) or CO(alkenyl).

[0165] In some embodiments, W + is selected from the group consisting of sodium, potassium, magnesium and ammonium cations. In some embodiments, Y - is selected from the group consisting of chloride, bromide, phosphate, dimethyl phosphate, methyl sulfate, ethyl sulfate, acetate and lactate.

[0166] In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. Similarly, in some embodiments, p is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. With respect to the PEG moiety, m can be an integer selected from 1 to 100, or 1 to 80, or 1 to 60, or 1 to 50, or 1 to 30, or 1 to 20, or 1 to 10, or 5 to 30, or 5 to 20, or 5 to 10. Further with respect to the PEG moiety, q can be an integer selected from 0 to 16, or 0 to 8, or 0 to 4, or 0 to 2. In some embodiments, q = 1. In other embodiments, 1 = 0.

[0167] In some embodiments, Z 1 is NR 2 R 3 、NR 2 -(CH2) n -NR 4 R 5 、NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - 、NR2 -(CH2) n -O(PO3H) - W + 、NR 2 -(CH2) n -Si(R 7 )3、NR 2 -(CH2) n -SR 8 、NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + 、NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R 7 )3、NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 、O(CH2) n -NR 4 R 5 、O(CH2) n -N + R 4 R 5 R 6 Y - 、O(CH2) n - - O(PO3H) - W + 、O(CH2) n -Si(R 7 )3、O(CH2) n -SR 8 、O(CH2) n -NR4 -(CH2) p -NR 9 R 10 、O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、O(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + Or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3, and Z 2 =Z 1 is as follows.

[0168] In some embodiments, one of Z 1 and Z 2 is NR 2 R 3 、NR 2 -(CH2) n -NR 4 R 5 、NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - 、NR 2 -(CH2) n -O(PO3H) - W + 、NR 2 -(CH2) n -Si(R 7 )3、NR 2 -(CH2) n -SR 8 Or NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 and the other is Z 1 and Z 2The other one of them is OR 1 or Z 1 is NR 2 R 3 NR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - NR 2 -(CH2) n -O(PO3H) - W + NR 2 -(CH2) n -Si(R 7 )3, NR 2 -(CH2) n -SR 8 or NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 and Z 2 =Z 1 is as follows

[0169] In some embodiments, one of Z 1 and Z 2 is NR 2 R 3 NR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - NR 2 -(CH2) n -O(PO3H) - W + NR 2 -(CH2) n -Si(R 7 )3, NR 2-(CH2) n -SR 8 or NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 wherein Z 1 and Z 2 one of which is OR 1 is as follows.

[0170] In some embodiments, Z 1 is NR 2 R 3 , NR 2 -(CH2) n -NR 4 R 5 , NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - , NR 2 -(CH2) n -O(PO3H) - W + , NR 2 -(CH2) n -Si(R 7 )3, NR 2 -(CH2) n -SR 8 , NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 wherein Z 2 =Z 1 is as follows.

[0171] In some embodiments, the modified form of PP IX is a compound of Formula II-B1,

Chemical formula

[0172] In some embodiments, Z 1 and Z 2 One of them is NR 2 R 3 and Z 1 and Z 2 The other one is OR 1 or or Z 1 =NR 2 R 3 and Z 2 =Z 1 and Each R 1 and R 2 is independently H, alkyl or substituted alkyl, R 3 is alkyl or substituted alkyl, Each R a 、R b 、R c 、R d 、R e and R f is independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl, M is 2H or a metal species, Substituted alkyl, substituted alkenyl and substituted alkynyl groups are independently substituted with one or more of OH, F, Cl, Br, I, CN and N3.

[0173] In some embodiments, R 1 is H, R 2 is H, and / or R 3 is alkyl. R 3 is, for example, (C1-C 12 )alkyl, (C1-C8)alkyl or (C1-C4)alkyl. In some embodiments, Z 1 and Z 2 One of them is NR 2 R 3 and the other one of Z 1 and Z 2 is OR 1It is. In other implementations, Z 1 =NR 2 R 3 wherein Z 2 =Z 1 is.

[0174] In some implementations, Z 1 and Z 2 one of them is NR 2 -(CH2) n -NR 4 R 5 or O-(CH2) n -NR 4 R 5 and Z 1 and Z 2 the other one of them is OR 1 or or Z 1 =NR 2 -(CH2) n -NR 4 R 5 or O-(CH2) n -NR 4 R 5 and Z 2 =Z 1 is R 5 is alkyl, substituted alkyl, or -(CH2) p -NR 9 R 10 and each R 1 R 2 R 4 R 9 and R 10 are independently H, alkyl or substituted alkyl, n is an integer selected from 1 to 16, p is an integer selected from 1 to 16, each R a R b R c R d R e and R fis independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl, M is 2H or a metal species, Substituted alkyl, substituted alkenyl and substituted alkynyl groups are independently substituted with one or more of OH, F, Cl, Br, I, CN and N3.

[0175] In some embodiments, R 1 is H, R 2 is H, and / or R 4 is H or alkyl. In some embodiments, R 4 is H, R 5 is alkyl. In some embodiments, R 4 and R 5 are alkyl. R 4 and / or R 5 is, for example, each independently, (C1-C 12 ) alkyl, (C1-C8) alkyl or (C1-C4) alkyl. In some embodiments, R 5 is -(CH2) p -NR 9 R 10 is. In some embodiments, R 9 and R 10 are alkyl, or R 9 is H, R 10 is alkyl. R 9 and / or R 10 is, for example, each independently, (C1-C 12 ) alkyl, (C1-C8) alkyl or (C1-C4) alkyl.

[0176] In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. In some embodiments, p is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4.

[0177] In some embodiments, Z 1 and Z 2 one of which is NR 2 -(CH2) n -NR 4 R 5 and the other of Z 1 and Z 2 is OR 1 In other embodiments, Z 1 =NR 2 -(CH2) n -NR 4 R 5 and Z 2 =Z 1 is

[0178] In some embodiments, Z 1 and Z 2 one of which is NR 2 -(CH2) n -Si(R 7 )3, O-(CH2) n -Si(R 7 )3, NR 2 -(CH2) n -SR 8 or O-(CH2) n -SR 8 and Z 1 and Z 2 the other of which is OR 1 or or Z 1 =NR 2 -(CH2) n -Si(R 7 )3, O-(CH2) n -Si(R 7 )3, NR 2 -(CH2) n -SR 8 or O-(CH2) n -SR 8 and Z 2 =Z 1 and each R 1 and R 2is independently H, alkyl or substituted alkyl, R 7 is alkyl, O(alkyl) or O(trisubstituted silyl), R 8 is H, alkyl, substituted alkyl or -(CH2) q -(CH2CH2O) m -R 13 wherein, R 13 is H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, CO(alkyl), CO(substituted alkyl), CO(alkenyl), CO(substituted alkenyl), CO(alkynyl) or CO(substituted alkynyl), n is an integer selected from 1 to 16, m is an integer selected from 1 to 100, q is an integer selected from 0 to 16, each R a R b R c R d R e and R f is independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl, M is 2H or a metal species, The substituted alkyl, substituted alkenyl and substituted alkynyl groups are each independently substituted with one or more of OH, F, Cl, Br, I, CN and N3.

[0179] In some embodiments, R 1 is H and / or R 2 is H. In some embodiments, R 7 is alkyl, O(alkyl) or O(trisubstituted silyl). The alkyl groups for R 1 R 2 and R 7 can each independently be (C1-C 12 )alkyl, (C1-C8)alkyl or (C1-C4)alkyl. In some embodiments, R 8is -(CH2) q -(CH2CH2O) m -R 13 where R 13 can be H, and m can be an integer selected from 1 to 20. In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. In some embodiments, q is an integer selected from 0 to 16, or 1 to 8, or 0 to 4, or 0 to 2. In some embodiments, q = 1. In other embodiments, q = 0.

[0180] In some embodiments, Z 1 and Z 2 one of which is NR 2 -(CH2) n -Si(R 7 )3, O-(CH2) n -Si(R 7 )3, NR 2 -(CH2) n -SR 8 or O-(CH2) n -SR 8 and the other of Z 1 and Z 2 is OR 1 In other embodiments, Z 1 = NR 2 -(CH2) n -Si(R 7 )3, O-(CH2) n -Si(R 7 )3, NR 2 -(CH2) n -SR 8 or O-(CH2) n -SR 8 and Z 2 = Z 1 In some embodiments, one of Z

[0181] and Z is NR2-(CH2) 1 and Z 2 -OP=O(OH)2 or O-(CH2) n -OP=O(OH)2 or O-(CH2)n -OP=O(OH)2, NR2-(CH2) n -OP=O(OH)O - W + or O-(CH2) n -OP=O(OH)O - W + and Z 1 and Z 2 the other of which is OR 1 or or Z 1 =NR2-(CH2) n -OP=O(OH)2 or O-(CH2) n -OP=O(OH)2, NR2-(CH2) n -OP=O(OH)O - W + or O-(CH2) n -OP=O(OH)O - W + and Z 2 =Z 1 and each R 1 and R 2 is independently H, alkyl or substituted alkyl n is an integer selected from 1 to 16 W + is an agriculturally acceptable cation each R a , R b , R c , R d , R e and R f is independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl M is 2H or a metal species Substituted alkyl, substituted alkenyl and substituted alkynyl groups are independently substituted with one or more of OH, F, Cl, Br, I, CN and N3

[0182] In some embodiments, R 1 is H and / or R2 is H. In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. W + may be selected from the group consisting of sodium, potassium, magnesium, and ammonium cations.

[0183] In some embodiments, Z 1 and Z 2 one of which is NR2-(CH2) n -OP=O(OH)2 or O-(CH2) n -OP=O(OH)2, NR2-(CH2) n -OP=O(OH)O - W + or O-(CH2) n -OP=O(OH)O - W + and the other of Z 1 and Z 2 is OR 1 In other embodiments, Z 1 =NR2-(CH2) n -OP=O(OH)2 or O-(CH2) n -OP=O(OH)2, NR2-(CH2) n -OP=O(OH)O - W + or O-(CH2) n -OP=O(OH)O - W + and Z 2 =Z 1 In some embodiments,

[0184] one of Z and Z 1 is NR 2 -(CH2) 2 -NR n R 4 R 5 R 6+ Y - or O-(CH2) n -NR 4 R 5 R 6+ Y- and Z 1 and Z 2 the other of which is OR 1 or or Z 1 =NR 2 -(CH2) n -NR 4 R 5 R 6+ Y - or O-(CH2) n -NR 4 R 5 R 6+ Y - and Z 2 =Z 1 and each R 1 and R 2 is independently H, alkyl or substituted alkyl, each R 4 , R 5 and R 6 is independently alkyl or substituted alkyl, n is an integer selected from 1 to 16, Y - is an agriculturally acceptable anion, each R a , R b , R c , R d , R e and R f is independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl, M is 2H or a metal species, Substituted alkyl, substituted alkenyl and substituted alkynyl groups are independently substituted with one or more of OH, F, Cl, Br, I, CN and N3.

[0185] In some embodiments, R 1 is H and / or R 2is H. In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. In some embodiments, R 4 , R 5 and R 6 are alkyl, and optionally R 4 =R 5 =R 6 . In some embodiments, Y - is selected from the group consisting of chloride, bromide, phosphate, dimethyl phosphate, methyl sulfate, ethyl sulfate, acetate and lactate.

[0186] In some embodiments, one of Z 1 and Z 2 is NR 2 -(CH2) n -NR 4 R 5 R 6+ Y - or O-(CH2) n -NR 4 R 5 R 6+ Y - , and the other of Z 1 and Z 2 is OR 1 . In other embodiments, Z 1 =NR 2 -(CH2) n -NR 4 R 5 R 6+ Y - or O-(CH2) n -NR 4 R 5 R 6+ Y - , and Z 2 =Z 1 .

[0187] In some embodiments, one of Z 1 and Z 2 is NR 2 -(CH2CH2O) m -R13 or O-(CH2CH2O) m -R 13 and Z 1 and Z 2 one of which is OR 1 or or Z 1 =NR 2 -(CH2CH2O) m -R 13 or O-(CH2CH2O) m -R 13 and Z 2 =Z 1 and each R 1 and R 2 are independently H, alkyl or substituted alkyl, R 13 is H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, CO(alkyl), CO(substituted alkyl), CO(alkenyl), CO(substituted alkenyl), CO(alkynyl) or CO(substituted alkynyl), m is an integer selected from 1 to 100, each R a , R b , R c , R d , R e and R f are independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl, M is 2H or a metal species, Substituted alkyl, substituted alkenyl and substituted alkynyl groups are independently substituted with one or more of OH, F, Cl, Br, I, CN and N3.

[0188] In some embodiments, R 1 is H and / or R 12is H. In some embodiments, m is an integer selected from 5 to 100, or 5 to 80, or 5 to 50, or 5 to 20, or 5 to 10. In some embodiments, R 13 is H, alkyl, alkenyl, CO(alkyl) or CO(alkenyl).

[0189] In some embodiments, Z 1 and Z 2 one of which is NR 2 -(CH2CH2O) m -R 13 or O-(CH2CH2O) m -R 13 and the other of Z 1 and Z 2 is OR 1 In other embodiments, Z 1 =NR 2 -(CH2CH2O) m -R 13 or O-(CH2CH2O) m -R 13 and Z 2 =Z 1 is the case.

[0190] In some embodiments, Z 1 and Z 2 one of which is a natural amino acid bonded to the compound by its amino group bonded to the alpha carbon, Z 1 and Z 2 the other of which is OR 1 or or Z 1 is a natural amino acid bonded to the compound by its amino group bonded to the alpha carbon, Z 2 =Z 1 is the case, each R 1 and R 2 is independently H, alkyl or substituted alkyl, each R a , R b, R c , R d , R e and R f are, independently, H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl, M is 2H or a metal species, Substituted alkyl, substituted alkenyl and substituted alkynyl groups are independently substituted with one or more of OH, F, Cl, Br, I, CN and N3.

[0191] In some embodiments, one of Z 1 and Z 2 is a natural amino acid bonded to the compound by its amino group bonded to the alpha carbon, and Z 1 and Z 2 the other of which is OR 1 .

[0192] In other embodiments, Z 1 is a natural amino acid bonded to the compound by an amino group bonded to the alpha carbon, and Z 2 =Z 1 .

[0193] In some embodiments, Z 1 is one of the natural amino acids, and Z 2 is OH, or Z 2 is one of the natural amino acids, and Z 1 is OH, or Z 1 is one of the natural amino acids, and Z 2 =Z 1 .

[0194] In some embodiments, Z 1 is glycine or L-valine, and Z 2 is OH, or Z 2 is glycine or L-valine, and Z 1 is OH, or Z 1 is glycine or L-valine, and Z 2 =Z 1 .

[0195] Non-limiting examples of modified PP IX photosensitizers include the following: [Chem.] [Chem.] [Chem.] [Chem.] [Chem.] [Chem.] or an agriculturally acceptable salt thereof.

[0196] Film-forming agent The film-forming composition described herein includes a film-forming agent capable of forming a film that is substantially impermeable to oxygen when at least a portion of the liquid carrier is removed after application to a plant. The film-forming agent can be any chemical compound that is impermeable to oxygen when in a dry or unhydrated state and forms a film that is permeable to oxygen when in a hydrated state. The film-forming agent can be a polymer. When the film-forming agent forms a film on a plant, all other components of the composition can be present within the film (i.e., the photosensitizer, antioxidants, and any other components of the composition). The film formed by the film-forming agent can slow the degradation of the photosensitizer by limiting the contact between the photosensitizer and oxygen molecules from the surrounding air. In some embodiments, the film slows the degradation of the photosensitizer when in a dry or unhydrated state by retarding the transmission of oxygen and can pass oxygen molecules at a higher rate when in a hydrated state.

[0197] As used herein, the term "film" refers to a layer of material (e.g., a layer of polymeric material) that can be deposited, formed, or otherwise present on a surface (e.g., the surface of a plant). The film-forming agent can be a hydrogel-forming polymer, and in such cases, the formed film can be a hydrogel. As used herein, the term "hydrogel" refers to a film formed by a network of hydrophilic and highly water-absorbent polymer chains. Polyvinyl alcohol is an example of a polymer that can form a hydrogel-type film.

[0198] In some embodiments, the film-forming agent is selected from the group consisting of ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, hydroxymethylpropyl cellulose, hydroxylpropyl cellulose polyvinylpyrrolidone, guar gum, nanocellulose, soy protein isolate, whey protein, collagen, starch, hydroxypropylated amylomaize starch, amylomaize starch, xylan, polyvinylidene chloride, polyvinyl alcohol (PVOH), ethylene vinyl alcohol (EVA), polyvinyl alcohol copolymers, and combinations thereof.

[0199] In some embodiments, the film-forming agent is a film-forming protein that forms a film that is substantially impermeable to oxygen when in the non-hydrated state. Non-limiting examples of such film-forming agents include soy protein isolate, whey protein, and collagen.

[0200] In some embodiments, the film-forming agent is a film-forming polysaccharide that forms a film that is substantially impermeable to oxygen when in the non-hydrated state. Non-limiting examples of such film-forming agents include guar gum and carboxymethyl cellulose.

[0201] In some embodiments, the film-forming agent is polyvinyl alcohol. The term "polyvinyl alcohol" is meant to encompass thermoplastic polymers derived from polyvinyl acetate through partial or complete hydroxylation (or hydrolysis). The degree of hydrolysis typically determines the physical, chemical, and mechanical properties of the polyvinyl alcohol. The degree of hydrolysis also typically affects the maximum moisture (water) uptake. Polyvinyl alcohol is highly hydrophilic and thus has good solubility in water. Films made from polyvinyl alcohol tend to have heat-sealing properties, oxygen, nitrogen, and carbon dioxide barrier properties in the non-hydrated state, and good adhesion to other hydrophilic surfaces. Polyvinyl alcohol films are biocompatible, biodegradable, and non-phytotoxic, making them well-suited for application to plants.

[0202] Polyvinyl alcohol can have an average molecular weight of from about 10 kDa to about 200 kDa or from about 50 kDa to about 100 kDa. For example, polyvinyl alcohol can have an average molecular weight of from about 13 kDa to about 23 kDa, or from about 31 kDa to about 50 kDa, or from about 89 kDa to about 98 kDa, or from about 146 kDa to about 186 kDa. Polyvinyl alcohol can have a degree of hydrolysis of 70% or more, or 80% or more, or 87% or more, or 87% - 89%, or 89% or more, or 89% - 99%, or 99% or more.

[0203] In some embodiments, the polyvinyl alcohol has an average molecular weight of about 50 kDa to about 100 kDa and a degree of hydrolysis of 99% or more. In some embodiments, the polyvinyl alcohol has an average molecular weight of about 13 kDa to about 23 kDa and a degree of hydrolysis of 98% or more. In some embodiments, the polyvinyl alcohol has an average molecular weight of about 31 kDa to about 50 kDa and a degree of hydrolysis of 98% to 99%. In some embodiments, the polyvinyl alcohol has an average molecular weight of about 89 kDa to about 98 kDa and a degree of hydrolysis of 99% or more. In some embodiments, the polyvinyl alcohol has an average molecular weight of about 146 kDa to about 186 kDa and a degree of hydrolysis of 99% or more. In some embodiments, the polyvinyl alcohol has an average molecular weight of about 31 kDa to about 50 kDa and a degree of hydrolysis of 87% to 89%. In some embodiments, the polyvinyl alcohol has an average molecular weight of about 89 kDa to about 98 kDa and a degree of hydrolysis of 87% to 89%. In some embodiments, the polyvinyl alcohol has an average molecular weight of about 146 kDa to about 186 kDa and a degree of hydrolysis of 87% to 89%.

[0204] In some embodiments, the polyvinyl alcohol can be selected from the group consisting of Kuraray Poval™, Kuraray Exceval™, Sekisui Selvol™, and combinations thereof.

[0205] When the film-forming agent includes a film-forming polymer, the film-forming polymer can be formulated with or without a plasticizer. It is understood that a plasticizer is an additive that increases the plasticity of a material. A plasticizer is typically a liquid or solid having low volatility. A plasticizer typically reduces the attractive forces between polymer chains and makes the polymer chains more flexible. It is understood that those skilled in the art will know which type of plasticizer can be used with any given film-forming polymer. For example, and without limitation, plasticizers commonly used for the film-forming agent polyvinyl alcohol include glycerol, ethylene glycol, propylene glycol, polyglycerol, low molecular weight polyethylene glycol, ethanol acetamide, ethanol formamide, and ethanolamine salts such as triethanolammonium acetate.

[0206] Antioxidant The film-forming compositions described herein can include antioxidants that can be included in the films formed by the film-forming agents. Antioxidants are more active against ROS than photosensitizers when in solution, in a dispersion, in a hydrogel-like environment, and / or in a film in a hydrated state. The function of the antioxidant is to slow the decomposition of the photosensitizer in solution before film formation and / or when the film is in a hydrated state after application of the film-forming composition to a plant. In some scenarios, the antioxidant does not slow the decomposition of the photosensitizer when the film is in a dry or non-hydrated state.

[0207] The antioxidant can be selected from the group consisting of phenolic antioxidants, chain-terminating antioxidants, physical quenchers of singlet oxygen, flavonoids, tocopherols, carotenoids, and antioxidant enzymes.

[0208] In some embodiments, the antioxidant is selected from the group consisting of vanillin (4-hydroxy-3-methoxybenzaldehyde), o-vanillin (2-hydroxy-3-methoxybenzaldehyde), vanillyl alcohol, tannic acid, gallic acid, propyl gallate, lauryl gallate, carvacrol, eugenol, thymol, sodium lignosulfonate, t-butyl-hydroxyquinone, butylated hydroxytoluene, butylated hydroxyanisole, alpha-tocopherol, D-alpha-tocopheryl polyethylene glycol succinate, retinyl palmitate, beta-carotene, erythorbic acid, sodium erythorbate, sodium ascorbate, ascorbic acid, glutathione, superoxide dismutase, catalase, sodium azide, 1,4-diazabicyclo[2.2.2]octane (DABCO), and combinations thereof.

[0209] In some embodiments, the antioxidant is a phenolic antioxidant that can be selected from the group consisting of gallate compounds or derivatives thereof, vanillin compounds or derivatives thereof, tannin compounds or derivatives thereof, lignin compounds or derivatives thereof, and combinations thereof. Without limitation, the phenolic antioxidants can be selected from the group consisting of vanillin (4-hydroxy-3-methoxybenzaldehyde), o-vanillin (2-hydroxy-3-methoxybenzaldehyde), vanillyl alcohol, tannic acid, gallic acid, propyl gallate, lauryl gallate, carvacrol, eugenol, thymol, sodium lignosulfonate, and combinations thereof.

[0210] In some embodiments, the antioxidant is a chain-end antioxidant that can be selected from the group consisting of thiol-containing compounds (e.g., glutathione), ascorbic acid or derivatives thereof, and combinations thereof.

[0211] In some embodiments, the antioxidant can be a physical quencher of singlet oxygen selected from the group consisting of sodium azide, 1,4-diazabicyclo[2.2.2]octane (DABCO), and combinations thereof.

[0212] In some embodiments, the antioxidant is a flavonoid such as an anthocyanin compound or a derivative thereof.

[0213] In some embodiments, the antioxidant can be a tocopherol selected from the group consisting of vitamin E (alpha-tocopherol) or a derivative thereof (e.g., vitamin E TPGS (D-alpha-tocopheryl polyethylene glycol succinate)).

[0214] In some embodiments, the antioxidant is a carotenoid that can be selected from the group consisting of beta-carotene, lutein, and combinations thereof.

[0215] In some embodiments, the antioxidant is an antioxidant enzyme that can be selected from the group consisting of catalase, superoxide dismutase, and combinations thereof.

[0216] Chelating agent In some embodiments, the compositions described herein can include a chelating agent (also referred to herein as a permeabilizing agent). In some scenarios, the photosensitizer compound reacts to light by generating ROS, while the chelating agent can increase the overall impact of the inhibition of microbial pathogen growth, for example, by increasing the permeability of the outer membrane of the microbial pathogen to the photosensitizer. It should be understood that the term "chelating agent" as used herein generally refers to a compound that can form several chelate bonds to one or several metals or ions.

[0217] In some embodiments, the chelating agent can include at least one carboxyl group, at least one hydroxyl group, at least one phenol group and / or at least one amino group or an agriculturally acceptable salt thereof. In some embodiments, the chelating agent can include an aminocarboxylic acid compound or an agriculturally acceptable salt thereof. The aminocarboxylic acid or an agriculturally acceptable salt thereof can include an aminopolycarboxylic acid or an agriculturally acceptable salt thereof. For example, the aminopolycarboxylic acid can include two amino groups and two alkylcarboxyl groups bonded to each amino group. The alkylcarboxyl group can be a methylcarboxyl group.

[0218] In some embodiments, the chelating agent is selected from the group consisting of aminopolycarboxylic acids, aromatic or aliphatic carboxylic acids, amino acids, phosphonic acids, and hydroxycarboxylic acids or agriculturally acceptable salts thereof.

[0219] In some embodiments, the compositions described herein include one or more aminopolycarboxylic acid chelating agents. Examples of aminopolycarboxylic acid chelating agents include, without limitation, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA), and ethylenediaminedisuccinate (EDDS), cyclohexanediaminetetraacetic acid (CDTA), N-(2-hydroxyethyl)ethylenediaminetriacetic acid (EDTA-OH) glycol ether diamine tetraacetic acid (GEDTA), alaninediacetic acid (ADA), alkoylethylenediaminetriacetic acids (e.g., lauroylethylenediaminetriacetic acid (LED3A)), aspartic acid diacetic acid (ASDA), aspartic acid monoacetic acid, diaminocyclohexane tetraacetic acid (CDTA), 1,2-diaminopropane tetraacetic acid (DPTA-OH), l,3-diamino-2-propanol tetraacetic acid (DTPA), diethylene triamine pentamethylene phosphonic acid (DTPMP), diglycolic acid, dipicolinic acid (DPA), ethanolamine diacetic acid, ethanol diglycine (EDG), ethylenediamine diglutaric acid (EDDG), ethylenediamine di(hydroxyphenylacetic acid (EDDHA), ethylenediamine dipropionic acid (EDDP), ethylenediamine disuccinate (EDDS), ethylenediamine monosuccinic acid (EDMS), ethylenediaminetetraacetic acid (EDTA), ethylenediamine tetrapropionic acid (EDTP), and ethylene glycol aminoethyl ester tetraacetic acid (EGTA) and their agriculturally acceptable salts (e.g., sodium salts, calcium salts and / or potassium salts).

[0220] One non-limiting example of a chelating agent is ethylenediaminetetraacetic acid (EDTA) or an agriculturally acceptable salt thereof. The aminocarboxylate salt can be, for example, a sodium salt or a calcium salt.

[0221] Another non-limiting example of a chelating agent is polyaspartic acid or an agriculturally acceptable salt thereof (i.e., polyaspartate), such as sodium polyaspartate. The molecular weight of the polyaspartate salt can be, for example, from 2,000 to 3,000.

[0222] Thus, the chelating agent can be a high molecular weight compound that can include aspartate units, carboxyl groups, and other features found in polyaspartate. Polyaspartate can be a copolymer having alpha and beta linkages that can be in various ratios (e.g., 30% alpha, 70% beta, randomly distributed along the polymer chain). One non-limiting example of sodium polyaspartate is Baypure® DS 100.

[0223] Other non-limiting examples of chelating agents include EDDS (ethylenediamine-N,N'-disuccinic acid), IDS (iminodisuccinic acid (N-1,2-dicarboxyethyl)-D,L-aspartic acid), isopropylamine, triethanolamine, triethylamine, ammonium hydroxide, tetrabutylammonium hydroxide, hexamine, GLDA (L-glutamic acid N,N-diacetic acid), or agriculturally acceptable salts thereof. The chelating agent can be metallized or non-metallized. In some implementations, IDS can be used as the tetrasodium salt of IDS (e.g., tetrasodium iminodisuccinate), which can be Baypure® CX100. In some implementations, EDDS can be used as the trisodium salt of EDDS. In some implementations, GLDA can be used as the tetrasodium salt of GLDA.

[0224] In some embodiments, the chelating agent can include one or more amino acid chelating agents. Examples of amino acid chelating agents include, without limitation, alanine, arginine, asparagine, aspartic acid, glutamic acid, glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, proline, serine, threonine, tyrosine, valine, or salts (e.g., sodium salts, calcium salts and / or potassium salts) and combinations thereof.

[0225] In some embodiments, the chelating agent can include one or more aromatic or aliphatic carboxylic acid chelating agents. Examples of aromatic or aliphatic carboxylic acid chelating agents include, without limitation, oxalic acid, succinic acid, pyruvic acid, malic acid, malonic acid, salicylic acid, and anthranilic acid, and salts thereof (e.g., sodium salts, potassium salts and / or potassium salts).

[0226] In some embodiments, the chelating agent can include one or more hydroxycarboxylic acid chelating agents. Examples of hydroxycarboxylic acid type chelating agents include, without limitation, malic acid, citric acid, glycolic acid, heptonic acid, tartaric acid and salts thereof (e.g., sodium salts, calcium salts and / or potassium salts).

[0227] It will be understood that one or more chelating agents can be provided as free acids, as agriculturally acceptable salts, or as combinations thereof. In some embodiments, each of the one or more chelating agents is applied as a free acid. In other embodiments, the chelating agent can be applied as a salt. Exemplary salts include sodium salts, potassium salts, calcium salts, ammonium salts, amine salts, amide salts, and combinations thereof. In still other embodiments, when two or more chelating agents are present, at least one of the chelating agents is applied as a free acid and at least one of the chelating agents is applied as a salt.

[0228] Liquid carrier The film-forming composition described herein includes a liquid carrier that can be present in an amount of 5 wt% to 99.9 wt% based on the weight of the film-forming composition applied to plants. In some embodiments, the liquid carrier can be an aqueous carrier.

[0229] It is understood that the term "liquid carrier" as used herein refers to a liquid that can solubilize and / or disperse the components of the combinations and compositions described herein. In some scenarios, the liquid carrier can include water. In other scenarios, the liquid carrier may not include water. In some embodiments, the liquid carrier can include an organic solvent that is partially or completely water-soluble, such as methanol, ethanol, propanol, or butanol, or a polyol such as glycerol, propylene glycol, polypropylene glycol. In some embodiments, the liquid carrier includes non-toxic and biodegradable compounds that can solubilize and / or disperse the components of the combinations and compositions described herein.

[0230] It is understood that the term "aqueous carrier" means a composition that includes 50 wt% or more water and, optionally, one or more water-soluble compounds and / or a water-insoluble solvent that can form an emulsion with water and / or can be dispersed in water. The aqueous carrier can solubilize and / or disperse film-forming agents, photosensitizers, and other components of the film-forming composition. When at least a portion of the aqueous carrier is removed, the film-forming agent forms a film that is substantially impermeable to oxygen and includes a photosensitizer and other components.

[0231] Suitable water-soluble compounds (including partially water-soluble compounds) can include, for example, methanol, ethanol, acetone, methyl acetate, dimethyl sulfoxide, or combinations thereof. In some implementations, the aqueous carrier can include 80 wt% or more water, or 90 wt% or more water, or 95 wt% or more water, or 99 wt% or more water, based on the total amount of the aqueous carrier. In some scenarios, depending on the components of the film-forming composition, using a water-soluble compound can help solubilize or disperse a photosensitizer compound in the aqueous carrier.

[0232] In some implementations, the aqueous carrier can include compounds that are water-insoluble, such as oils. The oil can be dispersed in water or can form a water-in-oil emulsion. The oil can be selected from the group consisting of mineral oils (e.g., paraffinic oils), vegetable oils, essential oils, and mixtures thereof. In some scenarios, and depending on the components of the film-forming composition, using an oil can help solubilize or disperse a photosensitizer compound in the aqueous carrier. In other implementations, the aqueous carrier does not include an oil.

[0233] Non-limiting examples of vegetable oils include oils containing medium-chain triglycerides (MCT) or oils extracted from nuts. Other non-limiting examples of vegetable oils include coconut oil, canola oil, soybean oil, rapeseed oil, sunflower oil, safflower oil, peanut oil, cottonseed oil, palm oil, rice bran oil, or mixtures thereof. Non-limiting examples of mineral oils include paraffinic oils, branched paraffinic oils, naphthenic oils, aromatic oils, or mixtures thereof.

[0234] Non-limiting examples of paraffinic oils include various grades of poly-alpha-olefins (PAO). For example, paraffinic oils can include HT60™, HT100™, High Flash Jet, LSRD™, and N65DW™. Paraffinic oils can include paraffins having a number of carbon atoms in the range of about 12 to about 50, or about 16 to 35. In some scenarios, the paraffin can have an average number of 23 carbon atoms. In some implementations, the oil can have a paraffin content of at least 80 wt%, or at least 90 wt%, or at least 99 wt%.

[0235] As used herein, the term "oil-in-water emulsion" refers to a mixture in which the oil is dispersed as droplets in water. In some implementations, the oil-in-water emulsion is prepared by a process that includes combining the oil, water, and any other components and applying shear until an emulsion is obtained.

[0236] It is to be understood that the liquid carrier typically enables the formation of a stable solution, suspension, and / or emulsion of the components of the film-forming composition.

[0237] Additives and adjuvants In some embodiments, the compositions described herein can include one or more agriculturally suitable adjuvants. Each of the one or more agriculturally suitable adjuvants can be independently selected from the group consisting of one or more activator adjuvants (e.g., one or more surfactants; e.g., one or more oil adjuvants, e.g., one or more penetrants) and one or more utility adjuvants (e.g., one or more wetting or spreading agents; one or more humectants; one or more emulsifiers; one or more drift control agents; one or more thickeners; one or more deposition agents; one or more water conditioners; one or more buffers; one or more defoamers; one or more UV blockers; one or more antioxidants; one or more fertilizers, nutrients, and / or micronutrients; and / or one or more herbicides). Exemplary adjuvants are provided in Hazen, J.L. Weed Technology 14:773-784 (2000), which is incorporated by reference in its entirety.

[0238] In some embodiments, the composition can also include a surfactant (also referred to as an emulsifier or dispersant). The surfactant can be selected from the group consisting of ethoxylated alcohols, polymeric surfactants, fatty acid esters, poly(ethylene glycol), ethoxylated alkyl alcohols, monoglycerides, alkyl monoglycerides, amphiphilic glycosides, and mixtures thereof. For example, the fatty acid ester can be a sorbitan fatty acid ester. The surfactant can include plant-derived glycosides such as saponins. The surfactant can be present as an adjuvant to aid in the coating of plant leaves. The surfactant can be an acceptable polysorbate-type surfactant (e.g., Tween 80), a nonionic surfactant blend (e.g., Altox™ 3273), or another suitable surfactant. In other embodiments, the liquid carrier does not include a surfactant.

[0239] In some embodiments, the poly(ethylene glycol) can include a poly(ethylene glycol) of the formula R 15 -O-(CH2CH2O) f -R 16 wherein each R15 and R 16 each independently is H, alkyl, substituted alkyl, aryl, substituted aryl, CO(alkyl) or CO(substituted alkyl), f is an integer selected from 1 to 100, and the substituted alkyl group is independently substituted with one or more of F, Cl, Br, I, hydroxy, alkenyl, CN and N3.

[0240] In some embodiments, the composition can include an antifoaming agent. Non-limiting examples of antifoaming agents include silicone oil, mineral oil, polydialkylsiloxane, fatty acids or their salts (e.g., salts with polyvalent cations such as calcium, magnesium and aluminum), alkynediols, fluoroaliphatic esters, perfluoroalkylphosphonic acids or their salts, perfluoroalkylphosphinic acids or their salts.

[0241] In some embodiments, the composition can include an antifreeze agent. Non-limiting examples of antifreeze agents include glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, 1,3-propanediol, 1,2-propanediol and polyethylene glycol.

[0242] In some embodiments, the composition can include a UV protecting substance that can stabilize at least some of the components of the composition from UV light. Non-limiting examples of UV protecting substances include hindered amine light stabilizers, titanium dioxide, zing oxide, nano-titanium dioxide, nano-zinc oxide, benzophenone, or combinations thereof.

[0243] Film-forming composition and combination Single composition In some embodiments, the film-forming agent, photosensitizer, antioxidant, and / or other optional components can be formulated as a single composition. In some scenarios, all components can be contained within a storage pack or container suitable for applying the composition to plants. In some scenarios, the single composition can be a concentrate that is diluted (e.g., with water or an additional liquid carrier) prior to application to the plant.

[0244] In some embodiments, the film-forming composition can include an antioxidant in an amount of about 0.001 wt% or more, or about 0.01 wt% or more, or about 0.05 wt% or more, or about 0.1 wt% or more, or about 0.25 wt% or more, or about 0.5 wt% or more, based on the total weight of the film-forming composition. In some embodiments, the film-forming composition can include an antioxidant in an amount of about 0.01 wt% to about 5 wt%, or about 0.01 wt% to about 1 wt%, or about 0.05 wt% to about 0.5 wt%, or about 0.1 wt% to 0.25 wt%, or about 0.1 wt% to about 0.2 wt%, based on the total weight of the film-forming composition.

[0245] In some embodiments, the film-forming composition can include a film-forming agent in an amount of about 0.01 wt% or more, or about 0.05 wt% or more, or about 0.1 wt% or more, or about 0.25 wt% or more, or about 0.5 wt% or more, or about 1 wt% or more, or about 5 wt% or more, based on the total weight of the film-forming composition. In some embodiments, the film-forming composition can include a film-forming agent in an amount of about 0.01 wt% to about 20 wt%, or about 0.01 wt% to about 10 wt%, or about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 1 wt%, or about 0.1 wt% to about 0.5 wt%, based on the total weight of the film-forming composition.

[0246] In some embodiments, the film-forming composition can include a photosensitizer in an amount of about 0.01 wt% or more, or about 0.05 wt% or more, or about 0.1 wt% or more, or about 0.25 wt% or more, or about 0.5 wt% or more, or about 1 wt% or more, or about 5 wt% or more, based on the total weight of the film-forming composition. In some embodiments, the film-forming composition can include a photosensitizer in an amount of about 0.01 wt% to about 10 wt%, or about 0.01 wt% to about 2 wt%, or about 0.05 wt% to about 2 wt%, or about 0.1 wt% to about 1 wt%, or about 0.1 wt% to about 0.5 wt%, based on the total weight of the film-forming composition.

[0247] In some embodiments, the liquid carrier is present in an amount of 5 wt% to 99.9 wt% based on the total weight of the film-forming composition. The liquid carrier is capable of solubilizing and / or dispersing the film-forming agent, the photosensitizer, and other components of the film-forming composition. When at least a portion of the liquid carrier is removed (e.g., by air drying), the film-forming agent forms a film that is substantially impermeable to oxygen and contains the photosensitizer and other components.

[0248] In some embodiments, the film-forming agent and the antioxidant can be present in the composition at a weight ratio of film-forming agent:antioxidant of about 1:1, or about 10:1, or about 20:1, or about 50:1, or about 500:1.

[0249] In some embodiments, the film-forming agent and the photosensitizer can be present in the composition at a weight ratio of film-forming agent:photosensitizer of about 1:1, or about 5:1, or about 10:1, or about 50:1, or about 100:1, or about 1000:1.

[0250] In some embodiments, the photosensitizer and the antioxidant can be present in the composition at a weight ratio of photosensitizer:antioxidant of about 0.1:1, or about 0.2:1, or about 1:1, or about 2:1, or about 10:1, or about 100:1.

[0251] Multiple - pack formulation Alternatively, a film - forming combination of a photosensitizer, a film - forming agent, an antioxidant, a liquid carrier, and / or any other suitable component can be provided as part of the multiple - pack formulation. In some embodiments, the components of the film - forming composition that ultimately exist on the plant can be separately packaged and / or stored prior to application to the plant, and the combination can be aggregated prior to application to the plant. In other embodiments, the components of the film - forming composition that ultimately exist on the plant can be separately packaged and / or stored prior to application to the plant and can be applied to the plant simultaneously or sequentially so as to form the film - forming composition upon application to the plant.

[0252] For example, the film - forming agent can be packaged by itself, in a dry state, or in a solution and / or dispersion in a liquid carrier, and the photosensitizer and antioxidant can be packaged together in a dry state or in a solution and / or dispersion in a liquid carrier. Any suitable additives and / or adjuvants can be added to either one or both of the packages.

[0253] In some embodiments, the antioxidant and the film - forming agent can be provided in a first pack, and the photosensitizer can be provided in a second pack. In other embodiments, the antioxidant and the photosensitizer can be provided in a first pack, and the film - forming agent can be provided in a second pack. In yet other embodiments, the film - forming agent and the photosensitizer can be provided in a first pack, and the antioxidant can be provided in a second pack. It is understood that the liquid carrier can be present in either or both of the first and second packs. Water or an additional liquid carrier can be added when combining the first and second packs to form the composition.

[0254] In yet other embodiments, the photosensitizer, film-forming agent, and antioxidant can each be provided in separate packs. It is understood that the liquid carrier can be present in one or all of the separate packs. Water or an additional liquid carrier can be added to one or all of the packs when forming the composition.

[0255] Mode of application The combinations and compositions described herein can be applied to plants in a variety of ways. For example, and without limitation, the combinations and compositions described herein can be applied by spraying, misting, watering, injection, dipping, or any other suitable method. The combinations and compositions can be applied to the leaves, roots, and / or stems of plants.

[0256] The plants to which the combinations and compositions are applied can be outdoors or indoors (e.g., in a greenhouse) where they are exposed to natural sunlight, or indoors where they are exposed to artificial light.

[0257] In some scenarios, the combinations and compositions described herein can be applied directly to plants as a preventive measure before infestation of the plants by pests. In other scenarios, the combinations and compositions described herein can be applied during or after infestation of the plants by pests.

[0258] Stability of the photosensitizer Here, referring to FIG. 1 and without being bound by theory, a schematic view of a film obtained from the film-forming combination or composition described herein is shown. In (a), the non-hydrated film stabilizes the photosensitizer against photodegradation by minimizing the interaction between the photosensitizer and oxygen. The photosensitizer generates less reactive oxygen species when the film is in a non-hydrated state due to the film's oxygen barrier properties. In (b), the hydrated film (or the film under high relative humidity) results in oxygen permeation and the generation of reactive oxygen species. The reactive oxygen species can then protect the plant from various biotic or abiotic stresses. In (c), the antioxidant embedded in the film removes excess reactive oxygen species in the film when the film is in a hydrated state, further protecting the photosensitizer from being photodecomposed.

[0259] Thus, the photosensitizer can be protected in two ways: by the film itself when the film is in a non-hydrated state such that the film-forming material is selected to be substantially impermeable to oxygen when the film is in a non-hydrated state, and by antioxidant substances when the film is in a hydrated state (or when the film is under high relative humidity) such that the film-forming material is selected to be permeable to oxygen when the film is in a hydrated state.

[0260] It should be understood that the meanings of the terms "hydrated state" and "non-hydrated state" are related to the properties of the film-forming agent and the characteristics of the film obtained from the film-forming agent. In fact, the first film obtained from the first film-forming agent will typically have different oxygen barrier properties from the second film obtained from the second film-forming agent. For example, a film obtained from a particular grade of polyvinyl alcohol is typically substantially impermeable to oxygen when the relative humidity is lower than about 50% RH or 60% RH. Thus, for a film made of a particular grade of polyvinyl alcohol, the expression "the film is in a hydrated state" may mean that "the film is in an environment with a relative humidity of 50% RH to 100% RH" or "the film is in an environment with a relative humidity of 60% RH to 100% RH". Similarly, the expression "the film is in a non-hydrated state" may mean that "the film is in an environment with a relative humidity lower than 50% RH" or "the film is in an environment with a relative humidity lower than 60% RH". It is understood that each film-forming agent can be provided in various grades, and each given grade can have a given "hydrated state" / "non-hydrated state" threshold that is specific to that grade. Those skilled in the art know how to measure the oxygen permeability at different relative humidity levels for a given film-forming agent and will determine the relative humidity at which each film obtained from a given film-forming agent may be in a "hydrated state" or a "non-hydrated state". One non-limiting example showing a method for measuring the effect of moisture content on the polyvinyl alcohol polymer structure is available in Journal of Coatings Technology and Research, 14, 1345-1355, 2017, which is hereby incorporated by reference in its entirety.

[0261] It should be understood that the meaning of the term "substantially impermeable to oxygen" as used herein refers to the ability of a material (e.g., a film) to block or slow the transmission of oxygen. In the context of this description, a film can be considered "substantially impermeable to oxygen" if the rate of oxygen transmission through the film is blocked or reduced. In the case where the film contains a photosensitizer, the film can be considered "substantially impermeable to oxygen" if the rate of oxygen-mediated photodegradation of the photosensitizer present in the film is lower than the rate of oxygen-mediated photodegradation of the same photosensitizer that does not exist in the film under the same conditions (temperature, RH%, pressure, etc.) in other respects. Alternatively, the film can be considered "substantially impermeable to oxygen" if the rate of oxygen-mediated photodegradation of the photosensitizer present in the film is lower than the rate of oxygen-mediated photodegradation of the same photosensitizer present in a film known to have high permeability to oxygen (e.g., a silicone-based hydrogel) under the same conditions (temperature, RH%, pressure, etc.) in other respects. It should be understood that the term "impermeable" is not meant such that a film that is "substantially impermeable to oxygen" exceeds or falls below any particular standard measurement of impermeability.

[0262] It should also be understood that the transition between the "hydrated state" and the "non-hydrated state", and vice versa, of the film can be a sudden or continuous transition. For example, if a composition containing the film (e.g., in the hydrated state) is applied to a plant and air-dried in the ambient state, the film may gradually become non-hydrated (i.e., gradually change from the hydrated state to the non-hydrated state), and the oxygen impermeability of the film may gradually increase until an equilibrium value is reached.

[0263] When a photosensitizer, a film-forming agent, an antioxidant, a liquid carrier, and any other components are mixed to form a film-forming composition, the film-forming agent is typically solubilized or dispersed in the liquid carrier. In such cases, the antioxidant can protect the photosensitizer from being photodecomposed in the solution or dispersion by reacting with the reactive oxygen species formed in the solution or dispersion. When the film-forming composition is applied to a plant, at least a portion of the liquid carrier begins to be removed, for example, by air drying. As a portion of the liquid carrier dries, the film-forming agent begins to form a film containing all of the components of the film-forming composition. Before the film is formed, the antioxidant can protect the photosensitizer from being photodecomposed. When a film is formed on a plant and the liquid carrier is at least partially removed, an oxygen barrier is obtained when the film is formed, and the photosensitizer is protected from being photodecomposed when the contact between the photosensitizer and oxygen is limited.

[0264] Method for improving plant health In some implementations, a method for promoting plant health is provided. The method includes applying to a plant a combination or composition comprising a photosensitizer that generates reactive oxygen species in the presence of light and oxygen, wherein the photosensitizer is selected from the group consisting of porphyrins, reduced porphyrins, and combinations thereof, a film-forming agent, an optional antioxidant, and a liquid carrier in which the photosensitizer, the film-forming agent, and the optional antioxidant are solubilized and / or dispersed.

[0265] The method can further include removing at least a portion of the liquid carrier from the applied composition (i.e., after application to the plant) to form a film that is substantially impermeable to oxygen. Removing at least a portion of the liquid carrier from the applied composition can be carried out by any known technique. For example, without damaging the plant, exposing the plant to a low humidity environment, exposing the plant to heat, and / or exposing the plant to a flow of air, an inert gas or nitrogen. In some implementations, the plant is air-dried in ambient conditions. For example, removing at least a portion of the liquid carrier from the applied composition can include enabling the composition to dry naturally on the plant (e.g., dry naturally on the leaves). When the liquid carrier is removed from the applied composition, the film-forming agent forms a film on the plant. For example, the film-forming agent forms a film that is substantially impermeable to oxygen when the liquid carrier (e.g., an aqueous carrier) dries after the composition has been applied to the plant.

[0266] Microbial pathogens Microbial pathogens to which a composition containing a photosensitizer compound can be applied include fungal and bacterial pathogens. In such cases, the composition can be referred to as an "antimicrobial composition".

[0267] Fungal pathogens to which the antimicrobial composition can be applied include Alternaria solani, which can infect plants such as tomatoes and potatoes, Botrytis cinerea, which can infect grapes as well as soft fruit and bulb crops, or Sclerotinia homoeocarpa, which generally infects turfgrass. Other fungal pathogens in the Alternaria, Botrytis, or Sclerotinia genera may also be subject to the application of the antimicrobial composition. The antimicrobial composition can be applied to plants that are affected by or susceptible to pathogens that cause various plant diseases, such as Colletotrichum, Fusarium, Puccinia, Erysiphaceae, Cercospora, Rhizoctonia, Bipolaris, Microdochium, Venturia inaequalis, Monilinia fructicola, Gymnosporangium juniperi-virginianae, Plasmodiophora brassicae, Ustilago zeae, Phytophthora, Pythium, Fusarium oxysporum, Phytophthora infestans, Taphrina deformans, Powdery Mildew, Phragmidium spp., or other fungal pathogens.

[0268] Bacterial pathogens to which the antimicrobial composition can be applied include Gram-negative bacteria such as Erwinia amylovara, or other bacterial pathogens in the genus Erwinia that can infect woody plants. E. amylovara causes fire blight on various plants including pears, apples, and other Rosaceae crops. The antimicrobial composition can be applied to plants that are affected by or susceptible to pathogens that cause various plant diseases, such as Pseudomonas, Xanthomonas, Agrobacterium, Curtobacterium, Streptomyces, E. Coli, Xylella fastidiosa (which causes Olive Quick Decline Syndrome (OQDS) disease), or other bacterial pathogens.

[0269] It is also noted that the antimicrobial compositions described herein can have various inhibitory effects on microbial pathogens, depending on the type of plant and pathogen, as well as the state of microbial infection. While it is described herein that the antimicrobial composition can inhibit the growth of microbial pathogens on plants, such statements are not limiting and are to be understood to include, without limitation, the suppression of microbial pathogens, the prevention of microbial pathogens, the killing of microbial pathogens, or generally increasing the toxicity to microbial pathogens.

[0270] Abiotic stress As noted above, in some implementations, the photosensitizer compounds and compositions described herein can be used to increase the tolerance of plants to one or more abiotic stresses such as photooxidative conditions, drying (water deficit), excessive watering (flooding and submergence), extreme temperatures (cold, freezing, and heat), extreme levels of light (strong and weak), radiation (UV-B and UV-A), excessive Na + (sodium) salts, chemical factors (e.g., pH), mineral (metal and metalloid) toxicity, deficiency or excess of essential nutrients, gaseous pollutants (ozone, sulfur dioxide), wind, mechanical factors, and other stress factors.

[0271] Cold tolerance When the abiotic stress is low temperature stress, the application of a photosensitizer compound alone or in combination with additives such as oils, surfactants, and / or chelating agents can improve the cold hardiness of plants. That is, the application of the photosensitizer compound can enable the plant to withstand temperature conditions that are lower than those typically experienced in the optimal or natural growth state of the plant. Various types of low temperature stress are possible, such as unexpected frost (e.g., early autumn frost where healthy crops, fruits, grains, seeds, or leaves are still present on the plant, or late spring frost that occurs after spring plant growth has started), cooler than average growing seasons, colder than normal winter conditions, minimal winter snow accumulation, ice accumulation, etc.

[0272] It should be noted that what constitutes a low temperature stress state for one plant may not be a low temperature stress state for another plant. Referring to the USDA zone map, the low temperature stress state for a plant in zone 9 may actually be the natural growth state for a plant in zone 8. Similarly, the depth of snow accumulation required for the survival of one type of plant may not be required for a second type of plant. Thus, it is understood that various types of low temperature stress are possible depending on the type of plant in question.

[0273] The photosensitizer compounds, compositions or combinations described herein can be used to protect plants, including woody plants, non-woody plants and turfgrass, from frost damage. The frost can be, for example, an early frost such as before harvest, after harvest, and before dormancy. The frost can be, for example, a late frost after germination. The low temperature damage can also be winter kill induced by winter temperatures, resulting in the loss of viable branches or shoots and potentially leading to plant death. Plants treated with the photosensitizer compounds, compositions or combinations described herein can be frost or low temperature sensitive plants in that they are naturally sensitive to damage or injury from frost, freezing or low temperatures in economically or aesthetically significant amounts.

[0274] Increased resistance to cold stress can be exemplified by a delayed onset of dormancy. Plant dormancy can be induced by a decrease in air temperature, for example, the onset of cold stress. By increasing the plant's resistance to cold stress, plant dormancy can be delayed until it is induced by a further decrease in temperature.

[0275] The photosensitizer compounds, compositions or combinations described herein can be used by applying them periodically (e.g., at two or three-week intervals starting in the spring at dormancy break) and / or one or more treatments (e.g., two in the fall) to provide a response in reducing or delaying the dormancy period of a particular plant.

[0276] As used herein, the term "reducing the dormancy period" refers to a plant having a reduced dormancy period or an extended growth period compared to a control, e.g., an untreated plant.

[0277] In some embodiments, the harvesting step can be performed one week, one month, two months or more after the last application of the photosensitizer compounds, compositions or combinations described herein, and the active agent is still effective in reducing the effect of cold stress on the plant during the intervening period.

[0278] In some scenarios, the resistance to cold stress includes resistance to early or late frosts, or winter injury. In some scenarios, the photosensitizer compounds, compositions or combinations described herein can be used to protect early growth from low temperatures during temperature fluctuations (e.g., in early spring). In some scenarios, the photosensitizer compounds, compositions or combinations described herein can be used to protect plants from low temperatures during cold months (e.g., in winter).

[0279] In some scenarios, the photosensitizer compounds, compositions or combinations described herein can be applied by soil perfusion and / or leaf application (e.g., spraying until runoff) at the start or prior to exposure to low temperatures (e.g., in the fall when the trees have fully healthy and vigorous leaves). In some scenarios, the photosensitizer compounds, compositions or combinations described herein can be applied by soil perfusion and / or leaf application (e.g., spraying until runoff) during late fall and winter (e.g., for warm climates). In some scenarios, the photosensitizer compounds, compositions or combinations described herein can be applied by winter leaf application (e.g., spraying until runoff) following late fall soil perfusion in order to achieve maximum hardiness.

[0280] In some scenarios, the photosensitizer compounds, compositions or combinations described herein can be applied 1 to 4 times at intervals of 1 to 6 months (e.g., every 2 to 3 months). Further treatments can be applied in the spring and / or during the growth period in order to improve resistance to subsequent low temperature stress conditions.

[0281] Heat tolerance When the abiotic stress is heat stress, application of the photosensitizer compounds, compositions or combinations described herein can improve tolerance to high temperatures during the growth period. That is, application of the photosensitizer compounds, compositions or combinations described herein can enable the plant to withstand temperature conditions higher than those typically experienced in the optimal or native growth state of the plant. Heat stress can have various causes, such as lack of shade for plants that typically require a shaded growth state, or higher than normal soil and atmospheric temperatures.

[0282] Note that what constitutes a heat stress condition for one plant may not be a heat stress condition for another plant.

[0283] Photooxidative durability When the abiotic stress is photooxidative stress, the application of the photosensitizer compounds, compositions or combinations described herein can improve the tolerance to stressful light conditions during the period of increased generation of reactive oxygen species. That is, the application of the photosensitizer compounds, compositions or combinations described herein can enable the plant to withstand higher light exposure conditions (e.g., ultraviolet irradiation conditions) than would typically be experienced in the optimal or native growth state of the plant. Photooxidative stress can have various causes, such as strong light conditions or certain types of lighting that induce the formation of free radicals.

[0284] Note that what constitutes a photooxidative stress state for one plant may not be a photooxidative stress state for another plant.

[0285] Shade tolerance Shade stress, or "low light (LL) stress", can be a problem that affects plant growth and quality. When the abiotic stress is shade stress, the application of the photosensitizer compounds, compositions or combinations described herein can improve the shade tolerance of the plant. That is, the application of the photosensitizer compounds, compositions or combinations described herein can enable the plant to withstand shade conditions for plants whose optimal or native growth state typically requires partial or full sunlight exposure. Various types of shade stress are possible, such as prolonged overcast days, excessive growth of adjacent plants or trees that create shade for the plant, or lack of availability of sunny planting locations.

[0286] Shade can be a recurring problem. For example, during certain months of the year, a structure near a plant may create shade for the plant and cause shade stress. As the Earth moves over the course of a year, the structure may not create any shade for the plant during another set of months, and then the situation can repeat during the next annual cycle. In such cases, the photosensitizer compounds, compositions, or combinations described herein can be applied to the plant before the start of the period of shade stress and can also be applied during the period of shade stress. Damage to the plant that would typically occur due to the period of shade stress can be prevented or reduced.

[0287] Since some plants have requirements for shade as part of their optimal growth state, the shade condition is not considered an abiotic stress condition for many types of plants. It should also be noted that what constitutes a shade stress condition for one plant may not be a shade stress condition for another plant.

[0288] Drought tolerance Drought can be defined as the lack of rainfall or irrigation for a period of time sufficient to deplete the soil moisture and damage the plant. Drought stress occurs when the water loss from the plant exceeds the plant's ability to absorb water through its roots and / or when the plant's water content is reduced sufficiently to interfere with normal plant processes. Since the plant's need for water can vary depending on plant type, plant phenology stage, plant age, root depth, soil quality, etc., the severity of the effects of the drought condition can vary among plants.

[0289] The photosensitizer compounds, compositions or combinations described herein can be applied to plants before and / or during the onset of drying. Application of the photosensitizer compounds, compositions or combinations described herein can increase the resistance of plants to drying stress. Increasing resistance can include maintaining or improving the quality of the plant compared to untreated plants exposed to the same drying stress. Increasing resistance can include reducing the deterioration of the quality of the plant compared to untreated plants exposed to the same drying stress. If a plant does not receive adequate rainfall or irrigation, the resulting drying stress can reduce growth more than all other combined environmental stresses.

[0290] Note that what constitutes a drying stress condition for one plant may not be a drying stress condition for another plant.

[0291] Prevention of salt damage Salts can occur naturally in the growth environment of plants. Salt stress refers to the osmotic force applied to a plant when the plant is growing in saline soil or under other excessive salt conditions. For example, plants growing near salt water bodies can be exposed to salts present in the atmosphere or in the water used to water the plants. In another example, salts applied to the surfaces of roads, sidewalks and driveways during the winter to improve driving conditions can migrate and / or leach into the soil of plants growing nearby. Such increased salt content in the plant growth environment can result in salt stress that can damage the plants.

[0292] Application of the photosensitizer compounds, compositions or combinations described herein to plants can increase the resistance of the plants to salt stress and may prevent or reduce a decrease in the quality of the plants that would occur if untreated. The combination can be applied before or during the period of salt stress.

[0293] Note that what constitutes a salt stress condition for one plant may not be a salt stress condition for another plant.

[0294] Transplant shock durability Plants that are transplanted from one growth environment to another, for example, from a pot to a flower bed or a garden, can be exposed to transplant shock stress as a result of exposure to new environmental conditions such as wind, direct sunlight, or a new soil condition. Application of the photosensitizer compounds, compositions, or combinations described herein to the roots of plants can reduce the impact on the plants caused by transplantation. In some scenarios, inhibition of plant growth and / or development of transplanted plants may be reduced or prevented by application of the photosensitizer compounds, compositions, or combinations described herein.

[0295] Note that what constitutes a transplant shock stress state for one plant may not be a transplant shock stress state for another plant.

[0296] Durability against excessive water or waterlogging Plants require a certain volume of water for healthy plant growth and development, but exposure of plants to an excessive volume of water ("water stress") can damage the plants. Application of the photosensitizer compounds, compositions, or combinations described herein to plants before the onset of an excessive water condition can increase the resistance of the plants to water stress. The photosensitizer compounds, compositions, or combinations described herein can be applied during water stress, but dilution of the photosensitizer compounds, compositions, or combinations described herein can occur due to excessive water. Therefore, pretreatment prior to a period of excessive water can be more effective.

[0297] Note that what constitutes an excessive water stress state for one plant may not be an excessive water stress state for another plant.

[0298] Insecticidal activity In some embodiments, the compounds and combinations described herein can be used to protect plants from insecticidal plant pests. As used herein, the term "insecticidal plant pest" or "insect pest" is to be understood to refer to insects and / or their larvae that are known to cause, or have the potential to cause, damage to plants. In some embodiments, the compounds and combinations described herein can induce photo-induced death in insect pests.

[0299] In some embodiments, the insect pest is selected from the order Hemiptera (the group of aphids, whiteflies, scale insects, mealybugs, stink bugs), Coleoptera (the group of beetles), Lepidoptera (the group of butterflies, moths), Diptera (the group of flies), Thysanoptera (the group of thrips), Orthoptera (the group of grasshoppers, locusts), Hymenoptera (the group of bees, ants), Blattodea (the group of cockroaches and termites), and the mite pest (spider mite).

[0300] Non-limiting examples of insect pests include, in the family Noctuidae (e.g., fall armyworm (Spodoptera fugiperda J.E. Smith)), caterpillars, (e.g., beet armyworm (Spodoptera exigua)), cutworms, loopers, (e.g., cabbage looper (Trichoplusia ni)) and heliothines, Spodoptera exigua Hubner, black cutworm (Agrotis ipsilon Hufnagel), and tobacco budworm (Heliothis virescens Fabricius), etc., larvae of the order Lepidoptera; borers, casebearers, webworms, coneworms, cabbageworms and skeletonizers, navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), and sod webworm (Herpetogramma licarsisalis Walker), etc., of the family Pyralidae (e.g., European corn borer (Ostrinia nubilalis Hubner)), leafrollers, budworms, seed worms, and fruit worms, grape berry moth (Endopiza viteanaClemens), the oriental fruit moth (Grapholita molesta Busck), and many other economically important Lepidoptera (e.g., the diamondback moth (Plutella xylostella Linnaeus), the pink bollworm (Pectinophora gossypiella Saunders), and the gypsy moth (Lymantria dispar Linnaeus)); leaf-feeding larvae and adults of Coleoptera including weevils (e.g., the boll weevil (Anthonomus grandis Boheman)) from the families Anthribidae, Bruchidae, and Curculionidae, the rice water weevil (Lissorhoptrus oryzophilus Kuschel), the granary weevil (Sitophilus granarius Linnaeus), the rice weevil (Sitophilus oryzae Linnaeus), the annual bluegrass weevil (Listronotus maculicollis Dietz), the bluegrass billbug (Sphenophorus parvulus Gyllenhal), the hunting billbug (Sphenophorus venatus vestitus), the Denver billbug (Sphenophorus cicatristriatus Fahraeus), the flea beetle, the cucumber beetle, the rootworm, the leaf beetle, the Colorado potato beetle (Leptinotarsadecemlineata), and leafminers in the family Chrysomelidae, western corn rootworm (Diabrotica virgifera virgifera LeConte); chafers and other beetles from the family Scaribaeidae (e.g., Japanese beetle (Popillia japonica Newman)), Oriental beetle (Anomala orientalis Waterhouse), northern masked chafer (Cyclocephala borealis Arrow), southern masked chafer (Cyclocephala immaculate Olivier), black turfgrass ataenius (Ataenius spretulus Haldeman), green June beetle (Cotinis nitida Linnaeus), Asiatic garden beetle (Maladera castanea Arrow), May / June beetle (Phyllophaga spp.), and European chafer (Rhizotrogus majalis Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae; flour beetles from the family Tenebrionidae; adult and nymphal Orthoptera including grasshoppers, crickets, and katydids (e.g., migratory grasshopper (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas)), American grasshopper (e.g., Schistocercaamericana Drury), desert locust (Schistocerca gregaria Forskal), migratory locust (Locusta migratoria Linnaeus), bush locust (Zonocerus spp.); adults and larvae of the order Diptera including leafminers, midges, fruit flies (Tephritidae), fruit flies (e.g., Oscinella frit Linnaeus), soil maggots; adults and nymphs of the orders Hemiptera and Homoptera such as plant bugs from the family Miridae, leafhoppers (e.g., Empoasca spp.) from the family Cicadellidae; planthoppers (e.g., corn plant hopper (Peregrinus maidis)) from the families Fulgoroidae and Delphacidae; treehoppers from the family Membracidae; chinch bugs (e.g., hairy chinch bug (Blissus leucopterus hirtus Montandon) and southern chinch bug (Blissus insularis Barber) and other seed bugs) from the family Lygaeidae; froghoppers from the family Cercopidae; squash bugs from the family Coreidae; red bugs and cotton stainers from the family Pyrrhocoridae; mealybugs (e.g., Planicoccus citri Risso) from the family Pseudococcidae, cicadas from the family Cicadidae; psyllids (e.g., Citrus psyllid Diaphorina citri) from Psyllidae, whiteflies (silverleaf whitefly (Bemisiaargentifolii)); cotton melon aphid (Aphis gossypii), pea aphid (Acyrthisiphon pisum Harris), cowpea aphid (Aphis craccivora Koch), black bean aphid (Aphis fabae Scopoli), melon or cotton aphid (Aphis gossypii Glover), apple aphid (Aphis pomi De Geer), spirea aphid (Aphis spiraecola Patch), foxglove aphid (Aulacorthum solani Kaltenbach), strawberry aphid (Chaetosiphon fragaefolii Cockerell), Russian wheat aphid (Diuraphis noxia Kurdjumov / Mordvilko), rosy apple aphid (Dysaphis plantaginea Paaserini), woolly apple aphid (Eriosoma lanigerum Hausmann), mealy plum aphid (Hyalopterus pruni Geoffroy), turnip aphid (Lipaphis erysimi Kaltenbach), cereal aphid (Metopolophium dirrhodum Walker), potato aphid (Macrosipum euphorbiae Thomas), peach-potato and green peach aphid (Myzus persicae Sulzer), lettuceaphid)(Nasonovia ribisnigri Mosley), root aphid, and gall aphid, corn leaf aphid (Rhopalosiphum maidis Fitch), bird cherry - oat aphid (Rhopalosiphum padi Linnaeus), wheat green aphid Aphids from the family Aphididae, such as greenbug (Schizaphis graminum Rondani), English grain aphid (Sitobion avenae Fabricius), spotted alfalfa aphid (Therioaphis maculata Buckton), black citrus aphid (Toxoptera aurantii Boyer de Fonscolombe), brown citrus aphid (Toxoptera citricida Kirkaldy), and green peach aphid (Myzus persicae); Phylloxera from the family Phylloxeridae; Mealybugs from the family Pseudococcidae; Scale from the families Coccidae, Diaspididae, and Margarodidae; Lace bugs from the family Tingidae; Stink bugs from the family Pentatomidae; Adults and immatures of the order Thysanoptera including onion thrip (Thrips tabaci Lindeman), flower thrips (Frankliniella spp.), and other leaf-feeding thrips. Agricultural pests also include mites from the family Tetranychidae: Twospotted spider mite (e.g., Tetranychus urticae Koch), Flat mites from Rutacea (e.g., citrus flat mite (Brevipalpus lewisi McGregor)); Rust and bud mites from the family Eriophyidae and other leaf-feeding mites, including other invertebrate arthropods.Economically important agricultural pest nematodes (e.g., root knot nematode in the genus Meloidogyne, lesion nematode in the genus Pratylenchus, and stubby root nematode in the genus Trichodorus) and members of the classes Nematoda, Cestoda, Trematoda, and Acanthocephala from the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida.

[0301] Type of plant The photosensitizer compounds and compositions described herein can be used against various types of plants. The plants can be non-woody crops, woody plants or turfgrasses. The plants can be selected from the group consisting of crop plants, fruit plants, vegetable plants, leguminous plants, cereal plants, forage plants, oilseed plants, field plants, horticultural plants, greenhouse plants, house plants, flower plants, turf plants, turfgrasses, trees such as fruit-bearing trees, and other plants that may be affected by microbial pathogens and / or one or more abiotic stresses. Some of the compounds described herein may exhibit a certain degree of toxicity against various harmful plant pests, in the absence or presence of light.

[0302] In some embodiments, the plant is a crop plant selected from the group consisting of sugarcane, wheat, rice, corn (maize), potato, sugar beet, barley, sweet potato, cassava, soybean, tomato, and leguminous plants (beans and peas).

[0303] In other embodiments, the plant is a tree selected from the group consisting of deciduous trees and evergreen trees. Examples of trees include, without limitation, fruit-bearing trees such as maple trees, citrus trees, apple trees, and pear trees, oak trees, paulownia trees, pine trees, and fir trees.

[0304] In yet other implementations, the plant is a shrub.

[0305] In yet other implementations, the plant is a fruit or nut plant. Non-limiting examples of such plants include acerola (Barbados cherry), atemoya, carambola (star fruit), rambutan, almond, anjous, cherry, nectarine, peach, pistachio, apple, avocado, banana, plantain, fig, grape, mango, olive, papaya, pear, pineapple, plum, strawberry, grapefruit, lemon, lime, orange (e.g., navel and Valencia), tangelo, tangerine, mandarin, as well as plants from the group of berries and small fruit plants.

[0306] In other embodiments, the plant is a vegetable plant. Non-limiting examples of such plants include asparagus, beans, beets, broccoli, Chinese broccoli, broccoli raab, bok choy, cabbage, cauliflower, Chinese cabbage (e.g., napa and mapa), Chinese mustard cabbage (gai choy), cavalo broccoli, collard, kale, kohlrabi, mizuna, mustard green, mustard spinach, rape green, celery, hyotao uri, Chinese waxgourd, citron melon, cucumber, gherkin, hyotan, cucuzza, hechima, Chinese okra, balsam apple, balsam pear, bitter gourd, Chinese cucumber, true cantaloupe, cantaloupe, casaba, crenshaw melon, golden pershaw melon, honeydew melon, honey gall, mango melon, Persian melon, pumpkin, summer squash, winter squash, watermelon, dasheen (taro), eggplant, ginger, ginseng root, herbs and spices (e.g., curly leaf basil, lemon balm, cilantro, Mexican oregano, mint), daikon (Japaneseradish)(daikon), lettuce, okra, pepper, potato, radish, sweet potato, Chinese artichoke (Japanese artichoke), corn and tomato are included.

[0307] In other implementations, the plant is a flowering plant, such as a rose, a flowering shrub or an ornamental plant. Non-limiting examples of such plants include flowering and foliage plants, including roses and other flowering shrubs, foliage ornamental plants and bedding plants, fruiting trees, non-fruiting trees, shade trees, ornamental trees, and shrubs (e.g., conifers, deciduous and broad-leaved evergreen trees, and woody ornamental plants), such as apple, cherry, peach, and pear trees.

[0308] In some implementations, the plant is an indoor plant. Non-limiting examples of such plants include chrysanthemum, dieffenbachia, dracaena, fern, gardenia, geranium, jade plant, palm, philodendron, and schefflera.

[0309] In some embodiments, the plant is a plant grown in a greenhouse. Non-limiting examples of such plants include ageratum, crown of thorns, dieffenbachia, dogwood, dracaena, fern, ficus, holly, lisianthus, magnolia, orchid, palm, petunia, poinsettia, schefflera, sunflower, aglaonema, aster, azalea, begonia, browallia, camellia, carnation, celosia, chrysanthemum, coleus, cosmos, crape myrtle, dusty miller, easter lily, fuchsia, gardenia, gerbera, hellichrysum, hibiscus leaf, hydrangea, impatiens, Japanese anemone, marigold, new guinea impatiens, nicotonia, philodendron, portulaca, reiger begonia, snapdragon, and zinnia.

[0310] In some embodiments, the plant can be a seed or a seedling. In such cases, the composition can be a seed coating composition. In other embodiments, the plant is a grown plant, and the composition is applied directly to the grown plant. It is understood that the grown plant has grown beyond the seed or seedling stage.

[0311] In some embodiments, the configurations described herein are applied to non-regenerable parts of the plant. The term "non-regenerable part of the plant" is understood to refer to a part of the plant that cannot grow or regenerate the whole plant when placed in a growth medium. In some embodiments, the compositions described herein can be applied to non-regenerable parts of a grown plant (e.g., the leaves of a grown plant).

[0312] Synergistic action of combinations In some scenarios, the combination may exhibit a synergistic response to inhibit the growth of microbial pathogens in plants. As used herein, the term "synergistic effect" or "synergistic" refers to the interaction of two or more components of a combination (or composition) such that the combined action of the two or more components of the combination (or composition) is greater than the sum of their individual actions. This may include the actions of two or more of a photosensitizer, a film-forming agent, an antioxidant, an oil, and a chelating agent in the context of this description. In some scenarios, the nitrogen-containing macrocyclic compound and the film-forming agent may be present in synergistically effective amounts. In some scenarios, the photosensitizer and the antioxidant may be present in synergistically effective amounts. In some scenarios, the film-forming agent and the antioxidant may be present in synergistically effective amounts. In some scenarios, the photosensitizer, the film-forming agent, and the antioxidant may be present in synergistically effective amounts.

[0313] In some scenarios, the approach shown in S.R. Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20 - 22 (1967) can be used to evaluate the synergistic effect. The expected effectiveness, E, can be expressed as E = X + Y(100 - X) / 100, where X is the effectiveness expressed as a percentage of the untreated control of the first component of the combination, and Y is the effectiveness expressed as a percentage of the untreated control of the second component of the combination. If the observed effectiveness is higher than the expected effectiveness, the two components are said to be present in synergistically effective amounts.

Example

[0314] General procedures and formulations Chlorophyllin - PVOH - tannic acid formulation The preparation of formulations that exhibit photo - stabilization of photo - sensitizers is described through the following exemplary methods. This example describes the preparation of a formulation of (0.1% magnesium chlorophyllin + 0.5% polyvinyl alcohol (89 kDa; 99% + hydrolyzed, PVOH89 - h)+0.05% tannic acid). First, a 5 wt% PVOH89 - h solution was prepared by slowly adding 5 g of PVOH89 - h solid to a beaker filled with 95 g of deionized water (dH2O) while mixing. This beaker was heated to a temperature of 95 °C and mechanically stirred for 1 hour. The dissolved solution was cooled and transferred to a clean glass bottle for use. Second, a 1 wt% tannic acid solution was prepared by dissolving 1 g of tannic acid (Sigma - Aldrich, St. Louis, MO) in 99 g of dH2O and used without further treatment. Third, a 1 wt% magnesium chlorophyllin, sodium salt stock solution was prepared by adding 1 g of magnesium chlorophyllin to 99 g of dH2O. To a 10 g glass vial, 1 g of 1% magnesium chlorophyllin was added to 8 g of dH2O, followed by 0.5 g of 5% PVOH89 - h and 0.5 g of 1% tannic acid solution. The vial was capped, mixed, and used within one week of preparation.

[0315] It is understood that other (photosensitizer + water - absorbent polymer + optional antioxidant + optional additional component) solutions can be formulated by the above method. The following formulations were prepared using the above method. All percentage values before the components of the formulation indicate weight - % values based on the total weight of the formulation. The percentage values 99%h, 89%h indicate the percentage of hydrolysis for PVOH. MgChln means magnesium chlorin e6 and AlChln means aluminum chlorin e6. - 0.1% MgChln+0.05% PVOH(89 kDa 99%h); - 0.1% MgChln+0.1% PVOH(89 kDa 99%h); - 0.1% MgChln+0.25% PVOH(89 kDa 99%h); - 0.1% MgChln+0.5% PVOH(89 kDa 99%h); -0.1% magnesium choline chloride + 0.5% PVOH (89 kDa, 99% hydrolyzed) + 0.01% tannic acid; -0.1% magnesium choline chloride + 0.5% PVOH (89 kDa, 99% hydrolyzed) + 0.05% tannic acid; -0.1% magnesium choline chloride + 0.5% PVOH (13 kDa, 99% hydrolyzed); -0.1% magnesium choline chloride + 0.5% PVOH (31 kDa, 99% hydrolyzed); -0.1% magnesium choline chloride + 0.5% PVOH (146 kDa, 99% hydrolyzed); -0.1% magnesium choline chloride + 0.5% PVOH (13 kDa, 89% hydrolyzed); -0.1% magnesium choline chloride + 0.5% PVOH (31 kDa, 89% hydrolyzed); -0.1% magnesium choline chloride + 0.5% PVOH (89 kDa, 89% hydrolyzed); -0.1% magnesium choline chloride + 0.5% PVOH (146 kDa, 89% hydrolyzed); -0.1% magnesium choline chloride + 0.5% PVOH (13 kDa, 99% hydrolyzed) + 0.05% tannic acid; -0.1% magnesium choline chloride + 0.5% PVOH (31 kDa, 99% hydrolyzed) + 0.05% tannic acid; -0.1% magnesium choline chloride + 0.5% PVOH (89 kDa, 99% hydrolyzed) + 0.05% tannic acid; -0.1% magnesium choline chloride + 0.5% PVOH (146 kDa, 99% hydrolyzed) + 0.05% tannic acid; -0.1% magnesium choline chloride + 0.5% PVOH (13 kDa, 89% hydrolyzed) + 0.05% tannic acid; -0.1% magnesium choline chloride + 0.5% PVOH (31 kDa, 89% hydrolyzed) + 0.05% tannic acid; -0.1% magnesium choline chloride + 0.5% PVOH (89 kDa, 89% hydrolyzed) + 0.05% tannic acid; -0.1% magnesium choline chloride + 0.5% PVOH (146 kDa, 89% hydrolyzed) + 0.05% tannic acid; -0.1% magnesium choline chloride + 0.5% PVOH (146 kDa, 99% hydrolyzed) + 0.05% tannic acid + 0.05% glycerol; -0.1% Magnesium Chloride + 0.5% PVOH (146 kDa, 99% hydrolyzed) + 0.05% Tannic Acid + 0.1% Glycerol; -0.1% Magnesium Chloride + 0.5% PVOH (146 kDa, 99% hydrolyzed) + 0.05% Tannic Acid + 0.05% Propylene Glycol; -0.1% Magnesium Chloride + 0.5% PVOH (146 kDa, 99% hydrolyzed) + 0.05% Tannic Acid + 0.1% Propylene Glycol; -0.03% Magnesium Chloride + 0.5% PVOH (89 kDa, 99% hydrolyzed); -0.03% Magnesium Chloride + 0.1% PVOH (89 kDa, 99% hydrolyzed); -0.03% Magnesium Chloride + 0.1% Vanillin; -0.03% Magnesium Chloride + 0.5% PVOH (89 kDa, 99% hydrolyzed) + 0.1% Vanillin; -0.03% Magnesium Chloride + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% Tannic Acid; -0.75% Magnesium Chloride + 0.5% Vanillin; -0.1% Magnesium Chloride + 0.5% PVOH (89 kDa, 89% hydrolyzed) + 0.05% Tannic Acid + 0.05% NaEDTA; -0.1% Magnesium Chloride + 0.5% PVOH (89 kDa, 89% hydrolyzed) + 0.05% Tannic Acid + 0.1% NaEDTA; -0.1% Magnesium Chloride + 0.5% PVOH (89 kDa, 89% hydrolyzed) + 0.05% Tannic Acid + 0.1% Pluronics® F - 127; -0.1% Magnesium Chloride + 0.5% PVOH (89 kDa, 89% hydrolyzed) + 0.05% Tannic Acid + 0.1% Breakthru® SD260 -0.1% Magnesium Chloride + 0.5% PVOH (89 kDa, 89% hydrolyzed) + 0.05% Tannic Acid + 0.1% Xiameter® OFX - 309; -0.1% Magnesium Chloride + 0.5% PVOH (89 kDa, 89% hydrolyzed) + 0.05% Tannic Acid + 0.1% Saponin -0.1% Magnesium Chloride + 0.5% PVOH (89 kDa, 89% hydrolyzed) + 0.05% Tannic Acid + 0.1% Morwet® D - 400; -0.1% Magnesium Chlorin e6 + 0.5% PVOH (89 kDa, 89% hydrolyzed) + 0.05% tannic acid + 0.1% Brij® O10; -0.1% Magnesium Chlorin e6 + 0.5% Galactasol 40HFDS + 0.05% tannic acid; -0.1% Magnesium Chlorin e6 + 0.5% carboxymethyl cellulose + 0.05% tannic acid; -0.1% Magnesium Chlorin e6 + 0.5% poly(vinyl alcohol-co-ethylene) (27 mol% ethylene) + 0.05% tannic acid; -0.1% Magnesium Chlorin e6 + 0.5% Solubon® PT401 + 0.05% tannic acid; -0.1% Chlorin e6 sodium salt + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% tannic acid; -0.1% Chlorin e6 dimethylaminoethyl + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% tannic acid; -0.1% Aluminum Chlorin e6 + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% tannic acid; -0.1% Magnesium Chlorin e6 + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% gallic acid; -0.1% Magnesium Chlorin e6 + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% propyl gallate; -0.1% Magnesium Chlorin e6 + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% vanillin; -0.1% Magnesium Chlorin e6 + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% vanillyl alcohol; and -0.1% Magnesium Chlorin e6 + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% Borresperse® NA.

[0316] Method A: Evaluate the photo-stability in the anhydrous state (also referred to as the "solid state"). Fifty microliters of each complex were pipetted into 12 wells of a 96-well clear-bottom black microplate (Thomas Scientific, Swedesboro, NJ) and dried to a thin film at 45 °C for 3 h using a dehydrator (Gourmia GFD1680). At the start of the experiment, the microplate was placed under a Heliospectra RX30 LED light array (Heliospectra, San Raphael, CA). The LED array was adjusted so that the microplate received an average light intensity of 1300 μmol / m 2 / s. The microplate was covered tightly with aluminum foil and peeled back at selected intervals to irradiate the film with light for either 0 h, 24 h, 48 h, or 72 h. At the end of the light irradiation, the contents of each well were redissolved in 100 μL of boiling dH2O and mixed until complete rehydration. Absorbance spectra scans were performed on the microplate (350–750 nm) using a plate reader (Spectramax M2E, Molecular Devices, San Jose, CA), and the peak intensities were monitored at the 24 h, 48 h, and / or 72 h time points and compared to the corresponding 0 h time point to determine the extent of photodegradation. The percentage of photosensitizer remaining after irradiation was calculated using the following equation, [Number]

[0317] where Abs t is the absorbance peak of the sample that has been exposed to light for t hours and Abs0 is the absorbance peak of the sample that has not been exposed to light. All data are presented as mean ± standard deviation.

[0318] Method B: Evaluating the photostability in solution (also referred to as the “liquid state”) Fifty microliters of each complex was pipetted into 12 wells of a 96-well clear-bottom black microplate (Thomas Scientific, Swedesboro, NJ), and subsequently 50 μL of dH2O was added. The samples were sealed with a clear adhesive film on the microplate to minimize evaporation of water. At the start of the experiment, the microplate was placed under a Heliospectra RX30 LED light array (Heliospectra, San Raphael, CA). The LED array was adjusted so that the microplate received an average light intensity of 1300 μmol / m 2 / s. The microplate was covered tightly with aluminum foil and peeled at selected intervals to irradiate the film with light for either 0 h, 2 h, 4 h, or 6 h. At the end of the light irradiation, the adhesive film was removed, and the absorbance of the samples was measured in each well using a plate reader (Spectramax M2E, Molecular Devices, San Jose, CA), redissolved in 100 μL of boiling deionized water (dH2O), and mixed until complete rehydration. An absorbance spectrum scan was performed on the microplate (350 - 750 nm), and the peak intensity was monitored at 2 h, 4 h, and 8 h time points and compared to the corresponding 0 h time point to determine the extent of photodegradation. The percentage of photosensitizer remaining after irradiation was calculated using the following equation, [Number]

[0319] where Abs t is the absorbance peak of the sample that has been exposed to light for t hours, and Abs0 is the absorbance peak of the sample that has not been exposed to light. All data are presented as mean ± standard deviation.

[0320] Example 1 The solid-state photostability of several formulations with different PVOH (89 kDa; >99% hydrolysis) contents was evaluated using Method A. The results are summarized in Table 1 below. [Table 1]

[0321] Example 2 The photostabilities of the solid and liquid states of several formulations having PVOH (146 kDa; over 99% hydrolyzed) and different antioxidant contents (phenolic antioxidant tannic acid) were evaluated using Method A and Method B. The results are summarized in Table 2 below.

Table 2

[0322] Example 3 The photostabilities of the solid and liquid states of several formulations having PVOH with different molecular weights and degrees of hydrolysis were evaluated using Method A and Method B. The results are summarized in Table 3 below.

Table 3

[0323] Example 4 The photostabilities of the solid and liquid states of several formulations having PVOH (146 kDa; over 99% hydrolyzed) and tannic acid with different plasticizer contents were evaluated using Method A and Method B. The results are summarized in Table 4 below.

Table 4

[0324] Commercially available PVOH is often compounded with plasticizers. This experiment shows that plasticizers have no particular effect on the stability of the solid and liquid states of photosensitizers.

[0325] Example 5 The control of the fungal plant pathogen Colletotrichum orbiculare ATC20767 (Cgm) against the host plant Nicotiana benthamiana after treatment with a formulation containing magnesium chlorophyllin, sodium salt with hydrogel polymer, polyvinyl alcohol 89 kDa (99%+ hydrolyzed), and the phenolic antioxidant vanillin was evaluated. The treatment was applied to N. benthamiana plants approximately 48 hours prior to inoculation to simulate photodegradation on the leaf surface. Subsequently, a spore suspension of Cgm was applied to the leaves. The plants were then exposed to light for a period of 24 hours and subsequently incubated in the dark until disease symptoms became apparent in the water-treated control plants. When the disease symptoms became apparent, the number of lesions / cm 2 To determine the leaf area, the lesions were counted and the leaf area was measured. Four replicate plants per treatment were used and the plants were randomized under the light source. The illumination was provided by LED light emitting approximately 450 μmol / m 2 / s of photosynthetically active radiation (PAR). The results are summarized in Table 5.

Table 5

[0326] Example 6 The control of the fungal plant pathogen Colletotrichum orbiculare ATC20767 (Cgm) against the host plant Nicotiana benthamiana after treatment with a formulation containing magnesium chlorophyllin, sodium salt with hydrogel polymer, polyvinyl alcohol 89 kDa (99%+ hydrolyzed), and the phenolic antioxidant tannic acid was evaluated. The treatment was applied to N. benthamiana plants approximately 48 hours prior to inoculation to simulate photodegradation on the leaf surface. Subsequently, a spore suspension of Cgm was applied to the leaves. The plants were then exposed to light for a period of 24 hours and subsequently incubated in the dark until disease symptoms became apparent in the water-treated control plants. When the disease symptoms became apparent, the number of lesions / cm 2To determine the leaf area, the lesions were counted and the leaf area was measured. Four replicate plants per treatment were used and the plants were randomized under the light source. Lighting was provided by LED light emitting approximately 450 μmol / m 2 / s of photosynthetically active radiation (PAR). The results are summarized in Table 6.

Table 6

[0327] Example 7 An experiment regarding the effect of the film-forming composition on the inhibition of the plant pathogen P. syringae in the host plant N. benthamiana was conducted in a growth chamber at 24 °C and a 16 / 8 hour light / dark photoperiod. Two days prior to inoculation, the chemical treatment was applied to N. benthamiana at the 5 - 6 leaf stage until runoff using a handheld spray bottle giving a fine spray. Plants sprayed with water were used as controls. Immediately after treatment, the plants were randomly shelved and exposed to LED light emitting approximately 450 μmol / m2 / s of photosynthetically active radiation (PAR) with a 12 hour light / 12 hour dark photoperiod. For inoculation, Pst from a glycerol stock was cultured on Tryptic Soy Agar (TSA) and incubated overnight at 30 °C. Bacterial cells were collected from the overnight culture, suspended in deionized water, diluted to 1×10^8 CFU / ml, and subsequently 0.02% (v / v) Silwet L-77 was added. The inoculum was then applied to the plants until runoff and the plants were covered with a clear plastic dome to maintain 100% relative humidity. The inoculated plants were randomly placed on the shelves of the growth chamber maintained at 24 °C and exposed to a combination of fluorescent and LED light emitting approximately 250 μmol / m 2 / s of PAR for 7 days with a 16 hour light / 8 hour dark photoperiod. The whole plant was evaluated for disease severity using a 0 - 100% rating scale. Disease symptoms included yellow lesions, leaf discoloration, leaf deformation, and stunted growth. Four replicates per treatment were used in the experiment.

Table 7

[0328] Example 8 One milliliter samples containing either 0.75% MgChln or 0.75% MgChln along with 0.5% vanillin in dH2O were prepared in 1.5 mL centrifuge tubes. These samples were wrapped with aluminum foil and stored in an oven at 54 °C for 2 weeks. After 2 weeks, the samples were removed from the oven at 54 °C or freezer at -20 °C and assayed using a UV visible plate reader (Spectramax M2E, Molecular Devices, San Jose, CA) with 12 technical replicates per sample. Degradation of MgChln as a result of storage at high temperature was determined by calculating the percentage of photosensitizer remaining using the following equation,

Number

[0329] where Abs t is the absorbance peak of the sample after 2 weeks of incubation at 54 °C, and Abs0 is the absorbance peak of the sample at the start of the experiment without being stored at 54 °C. All data are presented as mean ± standard deviation. The results are summarized in Table 8.

Table 8

[0330] Example 9 The photo-stabilities of several formulations with PVOH (89 kDa; >99% hydrolyzed) and various antioxidants in the solid and liquid states were evaluated using Method A and Method B. The results are summarized in Table 9 below.

Table 9

[0331] Example 10 The photo-stabilities of several formulations with PVOH (189 kDa; over 99% super-hydrolyzed), tannic acid, and various adjuvants in solid and liquid states were evaluated using Method A and Method B. The results are summarized in Table 10 below.

Table 10

[0332] Example 11 The photo-stabilities of several formulations with various film formers and MgChln tannate in solid and liquid states were evaluated using Method A and Method B. The results are summarized in Table 11 below.

Table 11

[0333] All film formers tested significantly improve the photo-stability of the photosensitizer in the solid state. The photo-stability of the photosensitizer in the liquid state is also improved using most of the tannic acid and film formers. Treatment with MgChln, poly(vinyl alcohol-co-ethylene), and tannic acid appears to provide similar photo-stability in the liquid state (within the error range) compared to MgChln alone.

[0334] Example 12 The photo-stabilities of several formulations with PVOH (189 kDa; over 99% super-hydrolyzed) and tannic acid and various adjuvants in solid and liquid states were evaluated using Method A and Method B. The results are summarized in Table 12 below.

Table 12

[0335] Here, Ce6-mixture-DMAE 15、17 The amide is the following two compounds,

Chemical formula

[0336] Examples 13-27 show that various Ce6 and PP IX compounds can improve plant health by inhibiting the growth of fungal pathogens, bacterial pathogens, and / or viruses, by protecting plants against abiotic stress, and / or by exhibiting insecticidal activity. These Ce6 and PP IX compounds can be used in the film-forming combinations and compositions described herein.

[0337] Example 13: Antifungal Activity of Modified Ce6 Photosensitizers Experiments were conducted to evaluate the antifungal activity of several Ce6 derivatives synthesized herein. The following method was used and the results are summarized in Tables 13A and 13B.

[0338] Agar Protocol: The control of Sclerotinia homoeocarpa using modified Ce6 was evaluated. Treatments were amended into Potato Dextrose Agar (PDA) at the desired concentrations. Then, 5 mm diameter plugs of Sclerotinia homoeocarpa isolates (a total of 3 isolates were tested) were inoculated in the center of the amended Petri dishes and incubated at 21 °C in the dark for 24 hours. After 24 hours, for the remainder of the experiment, one set of Petri dishes (triplicates) was placed in the dark and one set was placed under illumination (both at 21 °C). The radial growth of the fungus was monitored daily until the growth of S. homoeocarpa in unamended PDA reached the edge of the Petri dish. Illumination was provided by fluorescent lights emitting a photosynthetically active radiation (PAR) of about 180 μmol / m2 / s.

[0339] Bru protocol: Control of dollar spot fungus (Sclerotinia homoeocarpa) by modified chlorin was evaluated. Treatments were prepared in phosphate buffered saline (PBS) in 24-well plates at the desired concentrations (in duplicate for light / dark incubations). Then, 5 mm diameter plugs of Sclerotinia homoeocarpa isolates (a total of 3 isolates were tested) were inoculated into PBS and incubated in the dark at 21 °C for 2 hours. After 2 hours, one of the 24-well plates (with 3 replicates of the isolates) was placed in the dark and one 24-well plate was placed under illumination for 1 hour (both at 21 °C). After irradiation, the fungal plugs were removed from the PBS, blotted dry on sterile filter paper, and transferred to unmodified Potato Dextrose Agar (PDA). Radial growth of the fungus was monitored daily until the growth of S. homoeocarpa reached the edge of the Petri dish. Illumination was provided by LED light emitting photosynthetically active radiation (PAR) of approximately 1000 μmol / m2 / s.

Table 13

Table 14

[0340] The modified Ce6 compounds of Tables 13A and 13B can be used in the film-forming combinations and compositions described herein.

[0341] Example 14: Antibacterial Activity of Modified Ce6 Photosensitizer Experiments were conducted to evaluate the control of the Gram-negative bacterial plant pathogen Pseudomonas syringae pv. tabaci with modified Ce6. Treatments were prepared in phosphate-buffered saline (PBS) in 96-well plates at the desired concentrations. The bacterial suspension was inoculated into PBS and incubated at 28 °C in the dark for 30 minutes. After 30 minutes, the 96-well plates were placed under illumination (at 21 °C) for 1 hour. A separate plate prepared simultaneously was kept in the dark without illumination and used as a dark control. After irradiation, the bacterial suspension was serially diluted and 10 μL of each dilution was spread evenly onto Tryptic Soy Agar (TSA) plates and placed in the dark in an incubator at 28 °C for 48 hours. After 48 hours, the bacterial colonies were counted and the results were log-transformed (log colony-forming units (CFU) / mL). Relative inactivation was determined by taking the difference between logCFU (PBS control) and logCFU (treatment). Sample illumination was provided by LED light (Heliospectra RX30) emitting photosynthetically active radiation (PAR) of approximately 1000 μmol / m 2 / s.

[0342] The modified Ce6 evaluated was Ce6-mixture-DMAE 15、17 amide, Ce6-bis-DMAE 15、17 amide, and Ce6-mono-DMAE 15 amide. The results are presented in Table 14.

Table 15

[0343] All forms of Ce6 DMAE amide can be used (i.e., Ce6-mixture-DMAE 15、17 amide, Ce6-bis-DMAE 15、17 amide or Ce6-mono-DMAE 15It can be understood that the relative inactivation is obtained to be the same. This is because the data is presented as relative inactivation (i.e., the log ratio between the PBS control and the treatment). When using all forms of Ce6 DMAE amide, the treatment killed all bacteria without leaving colony-forming units, so the value was set to 1 CFU / mL so as not to generate mathematical errors. Therefore, the degree of inactivation depends on the control coefficient, and thus the values between treatments are the same. Nevertheless, these experiments show that all forms of Ce6 DMAE amide are active against Gram-negative bacteria.

[0344] The modified Ce6 compounds of Table 14 can be used in the film-forming combinations and compositions described herein.

[0345] Example 15 Effect of treatment on the tolerance of strawberry plants (Fragaria x ananassa) to salt stress In this example, the effect of the modified chlorin compound was tested against the strawberry plant (Fragaria x ananassa) cultivar (cv) Delizz. The experiment was conducted in a greenhouse. The test was designed to determine the activity of the compound against the tolerance of strawberry plants to salt stress.

[0346] In the experiment, strawberry plant seedlings were grown in 5-inch plastic pots filled with a specialized soil mixture (LC 1 Sunshine, Sungro Horticulture, Canada) and irrigated with water containing fertilizer at regular intervals. Strawberry plants at the stage of 4 - 5 leaves were treated with 3 foliar applications of different formulations using a handheld spray bottle to provide a uniform coating. The plants were sprayed at 7-day intervals. 24 hours after the first spray, the plants were exposed to salt stress by immersing the roots of the plants in a 15 mM sodium chloride solution. The salt level was gradually increased to 20 mM NaCl, and salt immersions were performed on a schedule of 5 - 7-day intervals. The plants were harvested 3 weeks after the last leaf spray. A surfactant was added to each treatment. The experiment was initiated with a completely randomized design having 5 replicates for each treatment.

Table 16

[0347] Strawberry plants treated with the tested chlorine compounds enhanced the plant's tolerance to salt stress.

[0348] The modified Ce6 compounds of Table 15 can be used in the film-forming combinations and compositions described herein.

[0349] Example 16 Effect of treatments on the tolerance of strawberry plants (Fragaria x ananassa) to drought stress In this example, the effect of the modified chlorine compound was tested on the strawberry plant (Fragaria x ananassa) cultivar Delizz. The experiment was conducted in a greenhouse. The test was designed to determine the activity of the compound on the tolerance of strawberry plants to drought stress.

[0350] In the experiment, strawberry plant seedlings were grown in 5-inch plastic pots filled with a specialized soil mixture (LC 1 Sunshine, Sungro horticulture, Canada) and irrigated with water containing fertilizer at regular intervals. Strawberry plants at the 4-5 leaf stage were treated with three leaf applications of different Suncor formulations using a handheld spray bottle to provide a uniform coating. The plants were sprayed at 7-day intervals. After the first leaf treatment and during the experimental period, the strawberry plants were exposed to a water regime (drought stress) where they were reduced to the wilting point (20 - 30% soil moisture content - SMC) and watered up to a maximum of 50% SMC. The plants were harvested 3 weeks after the last leaf spray. A surfactant was added to each treatment. The experiment was initiated with a completely randomized design having 7 replicates for each treatment.

Table 17

[0351] Strawberry plants treated with the chlorine compounds tested enhanced the plant's tolerance to drought stress.

[0352] The modified Ce6 compounds of Table 16 can be used in the film-forming combinations and compositions described herein.

[0353] Example 17 Effect of treatments on the tolerance of tomato plants (Solanum lycopersicum) cultivar Tiny Tim to heat stress The experiment was conducted in a growth chamber under controlled conditions. The test was designed to determine the activity of the compounds on the tolerance of tomato plants to heat stress.

[0354] In the experiment, the tomato cultivar Tiny Tim was grown in a greenhouse at a temperature of 24 - 26°C. Tomato seedlings were transplanted into 5-inch plastic pots containing a commercial soil mixture (LC 1 Sunshine, Sungro Horticulture, Canada). At the 5 - 6 leaf stage, the plants were treated with the tested solution using a hand-held spray bottle (leaf spray until runoff) to provide a uniform coating. 48 hours after spraying, the plants were transferred to a growth chamber and exposed to heat stress for 10 days. The tomato plants were watered regularly to avoid water deficit. After 10 days, the tomato plants were returned to the greenhouse and treated with the second test solution. 48 hours after the second spray, the plants were placed in the growth chamber and exposed to heat stress for an additional 10 days. Growth chamber conditions: 16 hours / 8 hours light / dark photoperiod; temperature of 19°C during the dark period; temperature during the light period - a 4-hour gradual increase in temperature from 19°C to 37°C, 8 hours at 37°C, and a gradual decrease in temperature to 19°C. Leaf treatment (spray) was applied twice. A surfactant was added to each treatment. The experiment was initiated in a completely randomized design with six replicates for each treatment.

Table 18

[0355] The novel chlorine formulation enhanced the tolerance of tomato plants to heat stress and increased plant biomass compared to the untreated control.

[0356] The modified Ce6 compounds of Table 17 can be used in the film-forming combinations and compositions described herein.

[0357] Example 18 Effect of treatments on the tolerance of Kentucky bluegrass (Poa pratensis) to salt stress Kentucky bluegrass (Poa pratensis) was grown under greenhouse conditions for approximately three weeks. After three weeks, the plants were sprayed with the formulation and left for 24 hours, after which the pots were placed in a 170 mM NaCl solution until the soil was saturated. The salt application was repeated again after 7 days for a total of two salt applications. Salt stress was evaluated based on a turf quality scale of 1 - 9, where 1 = dead, brown turf; 6 = minimally acceptable turf quality (based on golf course or sports field standards); and 9 = dense, dark green turf (healthy). The data are the average of five replicates.

Table 19

[0358] The modified Ce6 compounds of Table 18 can be used in the film-forming combinations and compositions described herein.

[0359] Example 19 Effect of Treatments on Silkworms Experiments were conducted to evaluate the toxicity of photosensitizer compounds against silkworm Bombyx mori (L.) larvae.

[0360] A colony of third-instar silkworm (Bombyx mori) larvae was purchased from a sales agent, Recorp Inc. (Ontario, Canada), and maintained on fresh mulberry leaves (Morus rubra) for two days prior to treatment.

[0361] Mulberry shoots were harvested from outdoor-grown trees and were not treated with any pesticides. The fresh mulberry shoots were washed with tap water and air-dried.

[0362] Small squash shoots (8 - 10 leaves) were excised from mature and healthy branches and inserted into 50 ml plastic vials filled with water. The vials were covered with lead and plastic mesh to prevent water evaporation and larval drowning. The host plant cuttings were sprayed with the tested solution until runoff, and the vials with the sprayed shoots were placed into 1 L clear plastic containers lined with filter paper.

[0363] Homogeneous silkworm larvae (3rd instar) were sprayed separately and placed onto the treated squash shoots in the containers. A soft fine paintbrush was used to handle the insects. The containers with the plant shoots and insects were covered with white mesh lead.

[0364] All treatments were applied as a fine spray using a 2 - ounce handheld spray bottle (ULINE, Canada). A water treatment was used as a control.

[0365] The containers with the shoots and insects were randomly placed in a metal rack equipped with LED lights and immediately irradiated with 450 μmol m -2 s -1 of light. The experiment was conducted in a plant growth chamber at a temperature of 24 - 26 °C and a photoperiod of 12 hours of LED light and 12 hours of dark period. The silkworms were fed with squash leaves treated for 48 hours. The food source was replaced once a day. A completely randomized design with four replicates for each treatment and 10 insects for each replicate was used in the experiment. The larvae were considered dead if no movement was detected after mechanical stimulation with a paintbrush. The number of surviving and dead insects was recorded. The insect mortality was evaluated up to 72 hours after treatment (HAT - hours after treatment). The squash leaves were evaluated for phytotoxicity symptoms.

[0366] Zn - Ce6 - mixture - DMAE 15、17 Amide and Pd - Ce6 - mixture - DMAE 15、17 Propylene glycol and Pluronic F - 127 surfactant were formulated into the amide to improve its solubility in water.

Table 20

[0367] Treatment with 0.1% Ce6 - mixture - DMAE 15、17 Amide and 0.1% Pd - Ce6 - mixture - DMAE 15、17 Amide + 0.5% propylene glycol + 0.1% Pluronic F127 caused larval mortalities of 57.5% and 35% respectively, and significantly reduced the larval weight.

[0368] The treated squash showed no visible symptoms of phytotoxicity. None of the tested formulations caused phytotoxicity on the leaves of the plants.

[0369] The modified Ce6 compounds of Table 19 can be used in the film - forming combinations and compositions described herein.

[0370] Example 20 Control of the fungal pathogen Cgm on Nicotiana benthamiana The control of the fungal plant pathogen Colletotrichum orbiculare ATC20767 (Cgm) on the host plant Nicotiana benthamiana after treatment with the modified chlorin e6 compound was evaluated. The treatment was applied to N. benthamiana plants approximately 2 hours before inoculation with a spore suspension of Cgm. The plants were then exposed to light for a period of 24 hours, followed by incubation in the dark until disease symptoms became apparent in the water - treated control plants. When the disease symptoms became apparent, the number of lesions / cm 2 To determine the leaf area, the lesions were counted and the leaf area was measured. Four replicate plants per treatment were used and the plants were randomized under the light source. The illumination was provided by LED light emitting photosynthetically active radiation (PAR) of approximately 180 μmol / m 2 / s. The results are shown in Tables 20A, 20B and 20C.

Table 21

[0371] Surfactants are added to the solution to increase the solubility of the compound and can spread on the leaf surface.

Table 22

[0372] In another experiment, the PEG-modified Ce6 compound was tested against Cgm.

Table 23

[0373] The modified Ce6 compounds of Tables 20A, 20B, and 20C can be used in the film-forming combinations and compositions described herein.

[0374] Example 21 Control of the bacterial pathogen Pst against Arabidopsis thaliana Arabidopsis thaliana plants were grown under a 12 h:12 h light:dark photoperiod, LED light (PAR 24 μmol m -2 s -1 ) at a temperature of 25 °C ± 3 °C and a relative humidity of 65%. After 3 weeks, the plants were sprayed with the formulation (50% diluted in water), dried for 2 h, and then sprayed with Pseudomonas syringae pv tabacci (diluted at OD 0.08 in 10 mM MgCl2). The plants were kept under a plastic dome until symptoms appeared. The disease severity was evaluated by counting the number of yellow leaves / plants. The data are the average values of three replicates.

Table 24

[0375] The modified Ce6 compounds of Table 21 can be used in the film-forming combinations and compositions described herein.

[0376] Example 22 Control of Pseudomonas syringae pv. tabaci against Nicotiana benthamiana The control of the bacterial plant pathogen Pseudomonas syringae pv. tabaci (Pst) against the host plant Nicotiana benthamiana after treatment with a modified chlorin e6 compound was evaluated. The treatment was applied to N. benthamiana plants approximately 2 hours prior to inoculation with a suspension of Cgm spores. The plants were then exposed to light for a period of 24 hours and subsequently incubated in the dark until disease symptoms became apparent in the water-treated control plants. When the disease symptoms became apparent, the number of lesions / cm 2 To determine the leaf area, the lesions were counted and the leaf area was measured. Four replicate plants per treatment were used and the plants were randomized under the light source. The illumination was provided by LED light emitting photosynthetically active radiation (PAR) of approximately 180 μmol / m 2 / s. The results are shown in Table 22.

Table 25

[0377] The modified Ce6 compounds of Table 22 can be used in the film-forming combinations and compositions described herein.

[0378] Example 23 Control of Rose aphid using a modified Ce6 compound Experiments were conducted to evaluate the toxicity of chlorine derivatives against the insect pest Rose aphid (Marcosiphum rosae). The experiments were conducted on rosebushes (cultivar Knockout, Double red) infested with aphids. The experiments were conducted at a plant nursery (Crop Inspection Service, California, Valley center, USA). The experimental plants were not exposed to pesticide treatments prior to the test.

[0379] The experimental rose plants were grown outdoors in 3-gallon black plastic pots filled with Sunshine #4 soil mix. The plants were watered daily and soluble fertilizer 20-20-20 at 200 ppm was applied twice a week.

[0380] The tips of rose plant shoots newly infested with aphid nymphs of the rose aphid were used in the experiment. The number of rose aphids in the colonies aggregating at the shoot tips was counted before treatment, and the treated shoots were covered with white 4×6-inch mesh organza bags (ULINE, USA) to avoid parasitism by natural enemies. The bags were fastened to the shoots during the test. At the start of the experiment, the aphid population (on the shoots) was considered to be homogeneous with 25 - 28 aphids per shoot. A completely randomized design was used with six replicate plants (one shoot per plant).

[0381] The treatments were applied using a 2-ounce plastic hand-held spray bottle (Natural Cylinder spray bottle, ULINE, Canada) that gave a uniform fine spray to the shoots of the plants. The rose shoots were thoroughly sprayed with the tested treatments and exposed to direct sunlight. A second application of the treatment was made 7 days after the first application using the same methodology.

[0382] The effect of the treatments on the insects was determined by counting the surviving insects 7 days after the first treatment and 14 days after the second treatment.

[0383] The plants were evaluated for phytotoxicity 6 days after each leaf spray.

Table 26

[0384] 0.1% Ce6-mono-3TP-PEG400 15 amide and 0.1% Ce6-mixture-DMAE 15、17 Treatment with the amide demonstrated excellent efficacy against the rose aphid and a suppressed insect population compared to the water control treatment.

[0385] The treated rose bush shoots showed no visible symptoms of phytotoxicity.

[0386] The modified Ce6 compounds of Table 23 can be used in the film-forming combinations and compositions described herein.

[0387] Example 24 Control of Cucumber Mosaic Virus on Pepper Plants Dwarf-type pepper "Golden baby belle hybrid" seedlings were transplanted into pots filled with pro-mix at the stage of 3-4 leaves and placed in a growth chamber with a temperature of 26 / 23 °C (day / night), 70% relative humidity, and a light intensity of 270 μmol m -2 s -1 with a light intensity of 270 μmol m. A formulation containing 0.1 wt% Ce6-mixture-DMAE 15、17 amide and surfactant was applied as a leaf application using a hand-held sprayer at 7, 14, 21, and 28 days after transplantation until the leaves were completely covered with the solution (about 2.5 mL / pot). The plants were watered sufficiently by manual irrigation and fertilized with 0.73 g of nitrogen m from a 28-8-18 complete fertilizer every two weeks -2 . Cucumber mosaic virus (CMV) inoculation was performed 2 hours after the third application. For inoculation, the leaf blades (about 1 g) of CMV-infected tobacco plants were ground in about 1 mL of PBS buffer (50 mM, pH 7) using a mortar and pestle, and a small amount of carborundum was added to the mixture. A Q-tip was applied to the upper surface of the three newly developed leaf blades at the tip of the pepper. A randomized block design with four replicates was used. The pots were randomly rearranged in the growth chamber twice a week. The severity of CMV disease incidence in the leaves was measured on days 19, 21, 28, 35, and at the end of the test. The disease severity was calculated as follows: Disease severity = number of infected leaves / 3 inoculated leaves + number of infected young leaves / total number of young leaves.

Table 27

[0388] The modified Ce6 compounds of Table 24 can be used in the film-forming combinations and compositions described herein.

[0389] Example 25 Effect of PP IX and modified PP IX against Pseudomonas syringae pv. tabaci In this example, the control of the gram-negative bacterial plant pathogen Pseudomonas syringae pv. tabaci using PP IX and modified PP IX was evaluated in the presence and absence of a chelating agent. Treatments were prepared in phosphate-buffered saline (PBS) in 96-well plates at the desired concentrations. Bacterial suspensions were inoculated into PBS and incubated for 30 minutes in the dark at 28 °C. After 30 minutes, the 96-well plates were placed under illumination (at 21 °C) for 1 hour. After irradiation, the bacterial suspensions were serially diluted and 10 μL of each dilution was spread evenly onto Tryptic Soy Agar (TSA) plates and placed in the dark in an incubator at 28 °C for 48 hours. After 48 hours, bacterial colonies were counted and the results were log-transformed (log colony-forming units (CFU) / mL). Relative inactivation was determined by taking the difference between log CFU (PBS control) and log CFU (treatment). Sample illumination was provided by LED light (Heliospectra RX30) emitting photosynthetically active radiation (PAR) of approximately 1000 μmol / m 2 / s. The results are summarized in Table 25.

Table 28

[0390] The PP IX and modified PP IX compounds of Table 25 can be used in the film-forming combinations and compositions described herein.

[0391] Example 26 Effects of PP IX and Modified PP IX on Dollar Spot Fungus In this example, the control of Sclerotinia homoeocarpa using PP IX and modified PP IX was evaluated. Treatments were prepared in phosphate buffered saline (PBS) in 24-well plates at the desired concentrations (in duplicate for light / dark incubations). Next, 5 mm diameter plugs of Sclerotinia homoeocarpa isolates (a total of 3 isolates were tested) were inoculated into PBS and incubated in the dark at 21 °C for 2 hours. After 2 hours, one of the 24-well plates (with 3 replicates of the isolates) was placed in the dark and one 24-well plate was placed under illumination for 1 hour (both at 21 °C). After irradiation, the fungal plugs were removed from the PBS, blotted dry on sterile filter paper, and transferred to unmodified Potato Dextrose Agar (PDA). The radial growth of the fungus was monitored daily until the growth of S. homoeocarpa reached the edge of the Petri dish. Illumination was provided by LED light emitting approximately 1000 μmol / m2 / s of photosynthetically active radiation (PAR). The results are summarized in Tables 26A and 26B.

Table 29

Table 30

[0392] The PP IX and modified PP IX compounds of Tables 26A and 26B can be used in the film-forming combinations and compositions described herein.

[0393] Example 27 Effects of PP IX and Modified PP IX on Colletotrichum orbiculare The control of the fungal plant pathogen Colletotrichum orbiculare ATC20767 (Cgm) against the host plant Nicotiana benthamiana after treatment with modified PP IX compounds was evaluated. The treatment was applied to N. benthamiana plants approximately 2 hours prior to inoculation with a spore suspension of Cgm. The plants were then exposed to light for a period of 24 hours and subsequently incubated in the dark until disease symptoms became apparent in the water-treated control plants. When the disease symptoms became apparent, the number of lesions / cm 2 To determine the leaf area, the lesions were counted and the leaf area was measured. Four replicate plants per treatment were used and the plants were randomized under the light source. The illumination was provided by LED light emitting photosynthetically active radiation (PAR) of approximately 180 μmol / m 2 / s. The results are shown in Table 27.

Table 31

[0394] The PP IX and modified PP IX compounds of Table 27 can be used in the film-forming combinations and compositions described herein.

Table 32-1

Table 32-2

Table 32-3

Table 32-4

Table 32-5

Table 32-6

[0395] All publications, patents, and patent documents cited in the foregoing specification are hereby incorporated by reference into this specification as if individually incorporated by reference. The compounds, compositions, methods, and uses described herein have been described with reference to various embodiments and techniques. However, one of ordinary skill in the art will understand that many variations and modifications can be made while remaining within the spirit and scope of the appended claims.

Claims

1. A composition for application to plants, comprising: a photosensitizer that generates reactive oxygen species in the presence of light and oxygen, wherein the photosensitizer is selected from the group consisting of porphyrins, reduced porphyrins, and combinations thereof; a film-forming agent selected from the group consisting of ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, hydroxymethylpropyl cellulose, guar gum, polyvinylpyrrolidone, nanocellulose, soy protein isolate, whey protein, collagen, starch, hydroxypropylated amylomaize starch, amylomaize starch, xylan, polyvinyl alcohol (PVOH), ethylene vinyl alcohol (EVA), polyvinyl alcohol copolymers, and combinations thereof; an antioxidant other than porphyrin; a liquid carrier in which the photosensitizer, the film-forming agent, and the antioxidant are solubilized and / or dispersed, wherein the film-forming agent comprises polyvinyl alcohol, and the polyvinyl alcohol has an average molecular weight of 50 kDa to 100 kDa and a degree of hydrolysis of 99% or more.

2. The composition according to claim 1, wherein the antioxidant is a phenolic antioxidant, and the phenolic antioxidant is selected from the group consisting of vanillin (4-hydroxy-3-methoxybenzaldehyde), o-vanillin (2-hydroxy-3-methoxybenzaldehyde), vanillyl alcohol, tannic acid, gallic acid, propyl gallate, lauryl gallate, carvacrol, eugenol, thymol, lignosulfonate, and combinations thereof.

3. The composition according to claim 1 or 2, wherein the photosensitizer is metallized with a metal selected from the group consisting of Mg(II), Zn(II), Pd(II), Sn(IV), Al(III), Pt(II), Si(IV), Ge(IV), Ga(III), In(III), Cu(II), Co(II), Fe(II), Mn(II), Co(III), Fe(III), Fe(IV), and Mn(III).

4. The composition according to any one of claims 1 to 3, wherein the photosensitizer is chlorin e6 or a modified chlorin e6, protoporphyrin IX (PP IX) or a modified PP IX, or meso-tetra-(4-sulfonatophenyl) porphyrin (TPPS).

5. The composition according to any one of claims 1 to 4, wherein the liquid carrier is an aqueous carrier or an oil-in-water emulsion.

6. The composition according to claim 5, wherein the oil contains poly-alpha-olefin (PAO).

7. The composition according to any one of claims 1 to 6, further comprising a chelating agent which is an aminopolycarboxylic acid or an agriculturally acceptable salt thereof.

8. The composition according to any one of claims 1 to 7, further comprising a surfactant, wherein the surfactant is selected from the group consisting of ethoxylated alcohols, polymeric surfactants, fatty acid esters, polyethylene glycols, ethoxylated alkyl alcohols, monoglycerides, alkyl monoglycerides and mixtures thereof.

9. The film-forming agent is present in an amount of 0.01% to 20% by weight based on the total weight of the composition, the photosensitizer is present in an amount of 0.01% to 10% by weight based on the total weight of the composition, and the antioxidant is present in an amount of 0.01% to 5% by weight based on the total weight of the composition. The composition according to any one of claims 1 to 8.

10. The composition according to any one of claims 1 to 9, which is for promoting the health of plants.

11. A method for promoting the health of a plant, comprising: applying the composition according to any one of claims 1 to 9 to the plant; and removing at least a portion of the liquid carrier from the composition for the film-forming agent to form a film on the plant.

12. The method according to claim 11, wherein removing at least a portion of the liquid carrier from the composition comprises at least one of exposing the plant to a low humidity environment, exposing the plant to heat, exposing the plant to a stream or air, an inert gas or nitrogen, and allowing the composition to dry naturally on the plant.

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