An oxygen-impermeable porphyrin photosensitizer film composition applied to plants

Abstract

There is provided a composition for application to plants. The composition comprises: 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 oxygen-impermeable when in a non-hydrated state; an antioxidant; and an aqueous carrier in which the photosensitizer, the film-forming agent, and the antioxidant are dissolved and / or dispersed. The composition is used for improving the health of plants.

Description

Technical Field

[0001] This technical field generally relates to photodynamic compositions for improving plant health, and more particularly to film-forming photodynamic compositions comprising photosensitizers applied to plants. Background Art

[0002] Photodynamic inhibition of microbial pathogens involves exposing a photosensitizer to light to generate reactive oxygen species (ROS), such as singlet oxygen, which can have a harmful effect on microbial pathogens. Photosensitizers generally degrade 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, there is provided a composition for application to a plant. The composition comprises: 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 oxygen-impermeable when in a non-hydrated state; an antioxidant; and a liquid carrier in which the photosensitizer, the film-forming agent, and the antioxidant are dissolved and / or dispersed.

[0004] In another aspect, there is provided the use of the composition described herein for improving the health of a plant.

[0005] In yet another aspect, there is provided a method for improving the health of a plant. The method comprises: applying to the plant a composition comprising: 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; an antioxidant; and an aqueous carrier in which the photosensitizer, the film-forming agent, and the antioxidant are dissolved or dispersed; and removing at least a portion of the aqueous carrier from the composition of the film-forming agent to form on the plant a film that is substantially oxygen-impermeable when in a non-hydrated state.

[0006] 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, guar gum, hydroxypropyl cellulose polyvinylpyrrolidone, nanocellulose, soy protein isolate, whey protein, collagen, starch, hydroxypropylated high amylose corn starch, high amylose corn starch, xylan, polyvinylidene chloride, polyvinyl alcohol (PVOH), ethylene vinyl alcohol (EVA), polyvinyl alcohol copolymers, and combinations thereof.

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

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

[0009] In some embodiments, the degree of hydrolysis of the polyvinyl alcohol is equal to or greater than 70%.

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

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

[0012] In some embodiments, when in a hydrated membrane, the antioxidant is more reactive towards reactive oxygen species than the photosensitizer.

[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, tert-butyl-hydroxyquinone, butylated hydroxytoluene, butylated hydroxyanisole, α-tocopherol, D-α-tocopherol polyethylene glycol succinate, retinyl palmitate, β-carotene, isoascorbic acid, sodium isoascorbate, 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, lignosulfonates, and combinations thereof.

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

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

[0021] In some embodiments, the photosensitizer is selected from the group consisting of chlorophyllide, bacteriochlorophyll, isobacteriochlorophyll, corrin, corphin, and mixtures thereof.

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

[0023] In some embodiments, the chlorophyllide is chlorophyllide e6 or a modified chlorophyllide e6.

[0024] In some embodiments, the photosensitizer comprises a 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 (PPIX) 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, the film-forming agent, and the antioxidant in the aqueous carrier.

[0029] In some embodiments, the aqueous carrier comprises an 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, rapeseed oil, soybean oil, canola 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 paraffin oil, branched paraffin oil, naphthenic oil, aromatic oil, and mixtures thereof.

[0033] In some embodiments, the oil comprises a poly-α-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'-dipentanedioic acid (EDDG) or an agriculturally acceptable salt thereof, ethylenediamine-N,N'-dimalonic 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 between about 0.01 wt% and about 20 wt% based on the total weight of the composition.

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

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

[0043] In some embodiments, the composition is a ready-to-use composition for application to plants.

[0044] In some embodiments, the composition is a concentrate to be diluted before application to plants.

[0045] In some embodiments, the plant is an adult plant.

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

[0047] In some embodiments, the membrane is substantially oxygen-impermeable when in an environment with a relative humidity below about 50% RH.

[0048] In some embodiments, the membrane is substantially oxygen-impermeable when in an environment with a relative humidity below about 60% RH.

[0049] In some implementations, the membrane is substantially oxygen-permeable when in a hydrated state.

[0050] In some embodiments, the membrane is substantially oxygen-permeable when in an environment with a relative humidity between 50% RH and 100% RH.

[0051] In some embodiments, the membrane is substantially oxygen-permeable when in an environment with a relative humidity between 60% RH and 100% RH.

[0052] In some embodiments, the composition is for application to plants by at least one of irrigation, spraying, misting, drenching, pouring, and dipping.

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

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

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

[0056] In some embodiments, the composition is for 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 plant.

[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 plant health involves increasing the plant's resistance to one or more abiotic stresses.

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

[0063] In some embodiments, promoting plant health involves controlling insect pests of the plant.

[0064] In some embodiments, the insect pests are selected from the group consisting of insects and insect larvae. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 is a schematic diagram of a film comprising a photosensitizer and an antioxidant in (a) a non-hydrated state and (b) a hydrated state. DETAILED DESCRIPTION

[0066] Photodynamic inhibition of microbial pathogens and / or insects that can infect 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 plant's resistance to damage caused by one or more abiotic stresses. Although the reactivity of the ROS generated by the photosensitizer is sufficient to help inhibit microbial pathogens and / or insects on the plant, their reactivity is also typically sufficient to degrade the photosensitizer compound. Thus, there is a need to stabilize the photosensitizer compound such that it is stable enough to be applied to the plant and generate ROS for a sufficient amount of time to effectively promote plant health.

[0067] This specification provides film-forming combinations and compositions for application to plants that include 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. When at least a portion of the aqueous carrier is removed after application to the plant, the film-forming agent forms a substantially oxygen-impermeable film. The antioxidant can be a phenolic antioxidant. The photosensitizer, film-forming agent, and antioxidant are dissolved and / or dispersed in the aqueous carrier. In one embodiment, the photosensitizer compound is a porphyrin or reduced porphyrin compound such as a chlorophyllin compound.

[0068] Exemplary porphyrin compounds are protoporphyrin IX or modified protoporphyrin IX or agriculturally acceptable salts thereof. Exemplary chlorophyllin compounds are chlorophyllin, modified chlorophyllin, or agriculturally acceptable salts thereof.

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

[0070] Definitions

[0071] Unless otherwise indicated, the following terms and phrases used herein are intended to have the following meanings.

[0072] When a trade name is used herein, it is intended to independently include the trade name product and the active ingredient of the trade name product.

[0073] 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 the compound of that formula and its salts, and optionally its agriculturally acceptable salts.

[0074] As used herein, the term "alkyl" means a hydrocarbon containing primary, secondary, tertiary or cyclic carbon atoms. By way of example, and not limitation, an alkyl may have from 1 to 20 carbon atoms (i.e., C1-C 20alkyl), 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, but are not limited to, 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).

[0075] As used herein, the term "alkenyl" means a hydrocarbon containing primary, secondary, tertiary or ring carbon atoms and having at least one unsaturated site, i.e., a carbon-carbon sp 2 double bond. By way of example and not limitation, alkenyl may have 2 to 20 carbon atoms (i.e., C2-C 20(alkenyl), having from 2 to 8 carbon atoms (i.e., C2-C8 alkenyl), having from 2 to 6 carbon atoms (i.e., C2-C6 alkenyl), or having from 2 to 4 carbon atoms (i.e., C2-C4 alkenyl). Examples of suitable alkenyls include, but are not limited to, ethene or vinyl (-CH═CH2), allyl (-CH2CH═CH2), cyclopentenyl (-C5H7), and 5-hexenyl (-CH2CH2CH2CH2CH═CH2).

[0076] As used herein, the term "alkynyl" means a hydrocarbon containing primary, secondary, tertiary, or cyclic carbon atoms and having at least one unsaturated site, i.e., a carbon-carbon sp triple bond. By way of example, and not limitation, an alkynyl may have from 2 to 20 carbon atoms (i.e., C2-C 20 alkynyl), having from 2 to 8 carbon atoms (i.e., C2-C8 alkynyl), having from 2 to 6 carbon atoms (i.e., C2-C6 alkynyl), or having from 2 to 4 carbon atoms (i.e., C2-C4 alkynyl). Examples of suitable alkynyls include, but are not limited to, ethynyl (-C≡CH) and propargyl (-CH2C≡CH).

[0077] As used herein, the term "alkoxy" may be interchanged with the term "O(alkyl)", wherein the "alkyl" group as defined above is attached to the parent molecule via an oxygen atom. By way of example, and not limitation, the alkyl portion of the O(alkyl) group may have from 1 to 20 carbon atoms (i.e., C1-C 20 alkyl), having from 1 to 8 carbon atoms (i.e., C1-C8 alkyl), having from 1 to 6 carbon atoms (i.e., C1-C6 alkyl), or having from 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 tert-butoxy (-O-C(CH3)3 or -OtBu). Similarly, "O(alkenyl)", "O(alkynyl)", and the corresponding substituted groups will be understood by those skilled in the art.

[0078] As used herein, the term "acyl" is intended to encompass several functional moieties such as "C═O(alkyl)", "C═O(alkenyl)", "C═O(alkynyl)", and their corresponding substituted groups, wherein the "alkyl", "alkenyl", and "alkynyl" groups are as defined above and are attached to O, N, S of the parent molecule via the C═O group. By way of example, and not limitation, the alkyl portion of the C═O(alkyl) group may have from 1 to 20 carbon atoms (i.e., C1-C 20(alkyl), having from 1 to 8 carbon atoms (i.e., C1-C8 alkyl), having from 1 to 6 carbon atoms (i.e., C1-C6 alkyl), or having from 1 to 4 carbon atoms (i.e., C1-C4 alkyl). Examples of suitable acyl groups include, but are not limited to, formyl (i.e., carboxyaldehyde group), acetyl, trifluoroacetyl, propionyl, and butyryl. Those skilled in the art will understand that the corresponding definitions apply to the "C=O(alkenyl)" and "C=O(alkynyl)" moieties. In this specification, "C=O(alkyl)", "C=O(alkenyl)", and "C=O(alkynyl)" may also be written as "CO(alkyl)", "CO(alkenyl)", and "CO(alkynyl)", respectively.

[0079] As used herein, the term "alkylene" means a saturated, branched or straight-chain or cyclic hydrocarbon group having two monovalent group centers derived by removing two hydrogen atoms from the same or two different carbon atoms of the parent alkane. By way of example and not limitation, alkylene may have from 1 to 20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 6 carbon atoms, or from 1 to 4 carbon atoms. Typical alkylene groups 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-).

[0080] As used herein, the term "alkenylene" means an unsaturated, branched or straight-chain or cyclic hydrocarbon group having two monovalent group centers derived by removing two hydrogen atoms from the same or two different carbon atoms of the parent alkene. By way of example and not limitation, alkenylene may have from 1 to 20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 6 carbon atoms, or from 1 to 4 carbon atoms. Typical alkenylene groups include, but are not limited to, 1,2-ethylene (-CH=CH-).

[0081] As used herein, the term "alkynylene" means an unsaturated, branched or straight-chain or cyclic hydrocarbon group having two monovalent group centers derived by removing two hydrogen atoms from the same or two different carbon atoms of the parent alkyne. By way of example and not limitation, alkynylene may have from 2 to 20 carbon atoms, from 2 to 10 carbon atoms, from 2 to 6 carbon atoms, or from 2 to 4 carbon atoms. Typical alkynylene groups include, but are not limited to, ethynylene (-C≡C-), propargyl (-CH2C≡C-), and 4-pentynyl (-CH2CH2CH2C≡C-).

[0082] As used herein, the term "aryl" means an aryl hydrocarbon group derived by removing a hydrogen atom from a single carbon atom of a parent aromatic ring system. By way of example and not limitation, an aryl can have 6 to 20 carbon atoms, 6 to 14 carbon atoms, or 6 to 10 carbon atoms. Exemplary aryls include, but are not limited to, groups derived from benzene (e.g., phenyl), substituted benzene, naphthalene, anthracene, and biphenyl.

[0083] As used herein, the term "arylalkyl" means an acyclic alkyl in which one of the hydrogen atoms bonded to a carbon atom (usually a terminal or sp 3 carbon atom) is replaced by an aryl. Exemplary arylalkyls include, but are not limited to, benzyl, 2-phenyleth-1-yl, naphthylmethyl, 2-naphthyleth-1-yl, naphthobenzyl, 2-naphthophenyleth-1-yl, and the like. By way of example and not limitation, an arylalkyl can include 7 to 20 carbon atoms, for example, an alkyl moiety having 1 to 6 carbon atoms and an aryl moiety having 6 to 14 carbon atoms.

[0084] As used herein, the term "arylalkenyl" means an acyclic alkenyl in which one of the hydrogen atoms bonded to a carbon atom (usually a terminal or sp 3 carbon atom, which can also be an sp 2 carbon atom) is replaced by an aryl. The aryl moiety of the arylalkenyl can include any aryl as described herein, and the alkenyl moiety of the arylalkenyl can include any alkenyl as described herein. An arylalkenyl can include 8 to 20 carbon atoms, for example, an alkenyl moiety having 2 to 6 carbon atoms and an aryl moiety having 6 to 14 carbon atoms.

[0085] As used herein, the term "arylalkynyl" means an acyclic alkynyl in which one of the hydrogen atoms bonded to a carbon atom (usually a terminal or sp 3 carbon atom, which can also be an sp carbon atom) is replaced by an aryl. The aryl moiety of the arylalkynyl can include any aryl as disclosed herein, and the alkynyl moiety of the arylalkynyl can include any alkynyl as disclosed herein. By way of example and not limitation, an arylalkynyl can include 8 to 20 carbon atoms, for example, an alkynyl moiety having 2 to 6 carbon atoms and an aryl moiety having 6 to 14 carbon atoms.

[0086] As used herein, the term "heterocycle" means a group that includes a covalently closed ring, where at least one of the atoms forming the ring is a heteroatom. By way of example and not limitation, a heterocycle can be formed from three, four, five, six, seven, eight, nine, or more than nine atoms. Any number of these atoms can be heteroatoms (i.e., a heterocycle can include one, two, three, four, five, six, seven, eight, nine, or more than nine heteroatoms). In a heterocycle that includes two or more heteroatoms, the two or more heteroatoms can be the same as or different from each other. A heterocycle can be substituted. The attachment to a heterocycle can be at a heteroatom or via a carbon atom. It should also be understood that, in this specification, the term "heterocycle" also encompasses "heteroaryl" groups.

[0087] As used herein, the term "protecting group" means a moiety of a compound that masks or modifies the nature of a functional group or the nature of the compound as a whole. The chemical substructure of a protecting group 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 protection / deprotection strategies are well known in the art. See: Protective Groups in Organic Chemistry, Theodora W. Greene (John Wiley & Sons, Inc., New York, 1991).

[0088] Unless otherwise specified, the term "substituted" as used herein with respect to alkyl, alkylene, alkoxy, alkenyl, alkynyl, alkenylene, aryl, alkynylene, etc., such as "substituted alkyl", "substituted alkylene", "substituted alkoxy", or "substituted O(alkyl)", "substituted alkenyl", "substituted alkynyl", "substituted alkenylene", "substituted aryl", and "substituted alkynylene" respectively means an alkyl, alkylene, alkoxy, alkenyl, alkynyl, alkenylene, aryl, and alkynylene in which one or more hydrogen atoms are each independently replaced by a non-hydrogen substituent.

[0089] Typical non-hydrogen substituents include, but are not limited to, -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 + RB 3. -NR B -(Alk)-OR B 、-NR B -(Alk)-OP(=O)(OR B )(O - )、-NR B -(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 B 2, wherein each X is independently a halogen: F, Cl, Br, or I; each R B is independently H, alkyl, aryl, arylalkyl, heterocycle, alkoxy such as poly(ethyleneoxy), PEG or poly(methyleneoxy), or a protecting group; each R C is independently alkyl, O(alkyl) or O(trisubstituted 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 connection with a group having two or more substitutable moieties (such as arylalkyl), the substituent may be attached to the aryl moiety, the alkyl moiety or both.

[0090] It should also be understood that the term "trisubstituted silyl" refers to a silyl group independently substituted by three functional groups selected from alkyl, alkenyl, alkynyl, aryl and arylalkyl. Non-limiting examples of trisubstituted silyls include trimethylsilyl and dimethylphenylsilyl.

[0091] As used herein, the term "PEG" or "poly(ethylene glycol)" is intended to encompass any water-soluble poly(ethylene oxide). Generally, substantially all or all of the monomeric subunits are ethylene oxide subunits, although PEG may contain different end-capping moieties or functional groups. The PEG chains of this specification may include one of the following structures: -(CH2CH2O) m - or -(CH2CH2O) m-1 CH2CH2-, depending on whether the terminal oxygen has been replaced, where 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 may be capped with a "capping group", which is typically a non-reactive carbon-containing group attached to the terminal oxygen or other terminal atom of PEG. Non-limiting examples of capping groups may 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).

[0092] Those skilled in the art will recognize that the substituents and other moieties of the compounds of this specification should be selected to provide agriculturally useful compounds that can be formulated into acceptable and stable agricultural compositions that can be applied to plants. Definitions and substituents of various genera and subgenera of the compounds of this specification are described and illustrated herein. Those skilled in the art should understand that any combination of the definitions and substituents described herein should not result in inoperable substances or compounds. It should also be understood that the phrase "inoperable substances or compounds" means a compound structure that violates relevant scientific principles (e.g., a carbon atom attached to more than four covalent bonds) or a compound that is too unstable to allow isolation and formulation into an agriculturally acceptable composition.

[0093] The selected substituents of the compounds of this specification can be present to a recursive degree. As used herein, a "recursive substituent" means that a substituent can enumerate another instance of itself. Due to the recursive nature of these substituents, in theory, a large number of compounds can exist in any given embodiment. For example, R x includes R y substituents. R y can be R. R can be W 3 . W 3 can be W 4 and W 4 can be R or include substituents that include R y . Those skilled in the art of organic chemistry understand that the total number of these substituents is reasonably limited by the desired properties of the expected compounds. These properties include, for example but not limited to, 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). Generally, in a given embodiment, each recursive substituent can independently occur 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0 times. For example, in a given embodiment, each recursive substituent can independently occur 3 times or less. Recursive substituents are an intended aspect of the compounds of this specification. Those skilled in the art of organic chemistry understand the generality of these substituents.

[0094] 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 that can enhance the resistance of a plant to one or more abiotic stresses. The term also refers to a salt that is converted or convertible in a plant, water, or soil to a compound or salt that exhibits pesticidal activity or that can enhance the resistance of a plant to one or more abiotic stresses. An "agriculturally acceptable salt" can be an agriculturally acceptable cation or an agriculturally acceptable anion. Non-limiting examples of agriculturally acceptable cations can include cations derived from alkali metals or alkaline earth metals and 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 halide anions, phosphate anions, alkylsulfate anions, and carboxylate anions. For example, agriculturally acceptable anions can include chloride, bromide, methylsulfate, ethylsulfate, acetate, lactate, dimethylphosphate, or polyalkoxylated phosphate anions.

[0095] As used herein with respect to a particular moiety of the compounds of the specification, the term "optionally substituted" means a moiety in which all substituents are hydrogen or in which one or more hydrogens of the moiety can be replaced by those substituents listed under the definition of the term "substituted" or by substituents as otherwise specified.

[0096] It is understood that this specification encompasses all enantiomers, diastereomers, and racemic mixtures, tautomers, polymorphs, and pseudopolymorphs of compounds within the scope of the formulas and compositions described herein and their agriculturally acceptable salts. All mixtures of such enantiomers and diastereomers are also within the scope of this specification.

[0097] The compounds of this specification and their agriculturally acceptable salts can exist as different polymorphs or pseudopolymorphs. As used herein, crystalline polymorphism means the ability of a crystalline compound to exist in different crystal structures. Crystal polymorphism can be caused by differences in crystal packing (packing polymorphism) or by differences in packing between different conformational isomers of the same molecule (conformational polymorphism). As used herein, crystalline pseudopolymorphism means the ability of a hydrate or solvate of a compound to exist in different crystal structures. Pseudopolymorphs of the compounds of this specification may exist due to differences in crystal packing (packing pseudopolymorphism) or due to differences in packing between different conformational isomers of the same molecule (conformational pseudopolymorphism). The description and depiction of the compounds of this specification are intended to include all polymorphs and pseudopolymorphs of the compounds and their agriculturally acceptable salts.

[0098] The compounds of the present specification and their agriculturally acceptable salts may also exist as amorphous solids. As used herein, an amorphous solid is a solid in which the positions of the atoms in the solid do not have long-range order. The description and depiction of the compounds of the present specification are intended to include all amorphous forms of the compounds and their agriculturally acceptable salts.

[0099] The modifier “about” when used in connection with a quantity includes the recited value and has the meaning specified by the context. For example, the modifier “about” can include the degree of error associated with the measurement of that quantity.

[0100] For agricultural use (i.e., application to plants), the salts of the compounds of the present specification are agriculturally acceptable salts. However, agriculturally unacceptable salts may also be used, for example, in the preparation or purification of agriculturally acceptable compounds. Accordingly, all salts, whether they are agriculturally acceptable salts or not, are understood to be within the scope of the present specification.

[0101] It should be understood that the compounds described herein can exist in their unionized, ionized, and zwitterionic forms and in combination with various amounts of water (e.g., stoichiometric water), such as in the form of hydrates.

[0102] Whenever a compound described herein is substituted by more than one identical designated group (e.g., “R 1 ” or “R 2 ”), it should be understood that these 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 an alkyl or aryl”, it should be understood that each R 7 can be independently selected from alkyls and aryls. Accordingly, Si(OR 7 )3 includes symmetric groups where all three R 7 are the same and asymmetric groups where at least one R 7 group is different from the other two R 7 groups or where each R 7 group is different. It should also be understood that this applies to all R q or Z q groups defined herein (e.g., q is selected from 1 to 17, a to f, or A to C). Only when “Z 1 = Z 2 ” is explicitly stated, the group “Z 1 ” should be understood to necessarily be the same as another group “Z 2 ”.

[0103] In some cases, the compounds described herein may also exist in tautomeric forms. Although generally only one delocalized resonance structure is depicted, all such forms are within the scope of this specification. For example, various tautomers may exist for the tetrapyrrole ring systems described herein, and all possible tautomeric forms thereof are within the scope of this specification.

[0104] As used herein, the term "growing medium" refers to any soil (of any composition) or soilless (e.g., hydroponic) medium suitable for growing and cultivating plants. The growing medium may further include any naturally occurring and / or synthetic substances suitable for growing and cultivating plants. As used herein, the phrase "any surface of the growing medium" or "the surface of the growing medium" refers to a surface that is directly exposed to natural light and / or simulated light and / or weather.

[0105] As used herein, the term "applying" refers to bringing into contact the surface of a plant or the surface of a growing medium with at least one combination or composition of this specification by any means known in the art (e.g., pouring, root bathing, soil drenching, drip irrigation, etc.), or bringing into contact the area below the surface of the growing medium with at least one combination or composition of this specification (e.g., by soil injection), or any combination thereof, or bringing a plant into direct contact with at least one combination or composition of this specification (e.g., spraying).

[0106] As used herein, the term "crop plant" refers to a non-woody plant that is grown, tended, and harvested within a period of one year or less as a source of food and / or energy. Non-limiting examples of crop plants include sugar cane, wheat, rice, corn (maize), potato, sugar beet, barley, sweet potato, cassava, soybean, tomato, and legumes (beans and peas).

[0107] As used herein, the term "woody plant" refers to a perennial woody plant (e.g., a tree) having a single stem or trunk and having lateral branches at a distance above the ground. Woody plants may 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, ash trees, pine trees, and spruce trees.

[0108] As used herein, the term "turfgrass" refers to cultivated grasses that provide ground cover, such as lawns or turf that are regularly mowed or trimmed to maintain a consistent height. Grasses belong to the Poaceae family, which is subdivided into six subfamilies, three of which include common turfgrasses: the Festucoideae subfamily of cool-season turfgrasses; and the Panicoideae subfamily and Eragrostoideae subfamily of warm-season turfgrasses. A limited number of species are widely used as turfgrasses, typically meeting the criteria of forming a uniform soil cover and tolerating mowing and traffic. Generally, turfgrasses have a compressed crown that facilitates mowing without cutting the growing point. In this document, the term "turfgrass" includes areas where one or more grass species are cultivated to form a relatively uniform soil cover, including blends that are combinations of different cultivars of the same species, or mixtures that are combinations of different species and / or cultivars.

[0109] Non-limiting examples of turfgrass include: Poa (e.g., Kentucky bluegrass), Agrostis (e.g., creeping bentgrass), Redtop, Festuca (e.g., red fescue), Lolium (e.g., annual ryegrass), Agropyron (e.g., crested wheatgrass), seashore paspalum, Bromus (e.g., Arizona brome), Distichlis (e.g., Sporobolus virginicus), Puccinellia distans, Cynosurus cristatus, Cynodon spp. (such as Cynodon dactylon, hybrid bermudagrass (e.g., common bermudagrass)), Zoysia (e.g., Zoysia japonica), St. Augustinegrass (e.g., Bitter Blue St. Augustinegrass), Eremochloa ophiuroides, Axonopus affinis, Paspalum notatum, Pennisetum clandestinum, Buchloe dactyloids, Paspalum vaginatum, Bouteloua gracilis, Bouteloua eriopoda, Bouteloua curtipendula, Sporobolus (e.g., Sporobolus virginicus), Sporobolus cryptandrus, Sporobolus heterolepis, Hordeum (e.g., Hordeum californicum), Hordeum vulgare, Hordeum brachyantherum, Alopecurus spp. (e.g., Creeping Foxtail and Meadow Foxtail), Stipa spp. (e.g., Needle & Thread), Elymus spp.)(e.g., Leymus arenarius), Buffelgrass (Cenchrus ciliaris), Big Quaking Grass (Briza maxima), Big Bluestem (Andropogon gerardii), Little Bluestem (Schizachyruim scoparium), Sand Bluestem (Andropogon hallii), Deer Grass (Muhlenbergia rigens), Eastern Gamagrass (Tripsacum dactyloides), Hilaria jamesii, Tufted Hairgrass (Deschampsia caespitosa), Indian Ricegrass (Oryzopsis hymenoides), Indian Grass (Sorghastrum nutans), Sand Lovegrass (Eragrostis trichodes); Weeping Lovegrass (Eragrostis curvula), California Melic (Melica californica), Prairie Junegrass (Koeleria pyramidata), Prairie Sandreed (Calamovilfa longifolia), Redtop (Agrostis alba), Reed Canarygrass (Phalaris arundinacea), Sloughgrass (Spartina pectinata), Leptochloa dubia, Bottlebush Squirreltail (Sitanion hystrix), Switchgrass (Panicum virgatum), and Purple Threeawn (Aristida purpurea).

[0110] As used herein, the phrase "promote the health of a plant" includes at least one of preventing diseases, disorders or damage caused by plant pests and increasing the abiotic stress resistance or tolerance of a plant. In other words, the phrase "promote the health of a plant" includes at least one of "preventing infection of a plant by one or more biological agents", "preventing infestation of a plant by one or more insects", and "increasing the resistance of a plant to one or more abiotic stresses".

[0111] As used herein, the phrase "preventing infection of a plant by a biological agent" means reducing, ameliorating or stabilizing the infection and / or any other unwanted disorders or side effects present caused by the combination of microbial pathogens or infestation of a plant by insects. Microbial pathogens can include fungi, bacteria (Gram-positive or Gram-negative), viruses, viroids, virus-like organisms, phytoplasmas, etc.

[0112] As used herein, the term "abiotic stress" refers to environmental conditions that have a negative impact on the growth, development, yield and yield quality of crops and other plants. Below optimal levels. Non-limiting examples of abiotic stress include, for example: photooxidative conditions, drought (water shortage), overwatering (waterlogging and submersion), extreme temperatures (low temperature, freezing and heat), extreme light levels (high and low), radiation (UV-B and UV-A), salinity due to excess Na + (alkalinity), 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 stressors.

[0113] As used herein, the term "increase stress resistance" (etc.) means an increase in the ability of a plant to survive or thrive under stress conditions. Enhanced resistance or tolerance can be specific to a particular stressor, such as drought, excess water, nutrient deficiency, salt, cold, shade or heat, or multiple stressors. In some cases, an increase in resistance to one or more abiotic stresses can be exemplified by a reduction in plant quality degradation compared to untreated plants subjected to the same stress. In other cases, an increase in resistance to one or more abiotic stresses can be exemplified by maintained or improved plant quality compared to untreated plants subjected to the same stress.

[0114] Photosensitizer compound

[0115] The compositions of the present specification include photosensitizer compounds that are capable of photodynamically inhibiting biological agents (i.e., microbial pathogens and / or insects) that may be present on a plant and / or that protect a plant from abiotic stress. The photosensitizer compounds react to light by generating reactive oxygen species (ROS).

[0116] Depending on the type of ROS generated, photosensitizers can be divided into two categories, namely type I photosensitizers and type II photosensitizers. On the one hand, when excited at an appropriate wavelength in the presence of oxygen, type I photosensitizers form short-lived free radicals by extracting or transferring electrons from the substrate. On the other hand, type II photosensitizers form a highly reactive oxygen state called "singlet oxygen", also referred to herein as "reactive singlet oxygen species". Singlet oxygen generally has a relatively long lifetime and can have a relatively large radius of action.

[0117] It should be understood that the photosensitizer compound can be metallized or non-metallized. When metallized, as in the case of various nitrogen-containing macrocyclic compounds complexed with metals, the metal can be selected to generate type I or type II photosensitizers in response to exposure. For example, when a chlorin-type compound is metallized with copper, the ROS generated is generally a type I photosensitizer. When the same chlorin-type compound is metallized with magnesium, the ROS generated is generally a type II photosensitizer. Both type I and type II photosensitizers can be used to achieve photodynamic inhibition of biological agents present on plants or to protect plants from abiotic stresses. In some cases, the photosensitizer compound is a type I photosensitizer. In other cases, the photosensitizer compound is a type II photosensitizer.

[0118] It should be understood that the term "singlet oxygen photosensitizer" as used herein refers to a compound that generates reactive singlet oxygen species when photoexcited. In other words, the term "singlet oxygen photosensitizer" refers to a photosensitizer in which the type II process defined above predominates compared to the type I process.

[0119] In some embodiments, the photosensitizer compound is a photosensitive nitrogen-containing macrocyclic compound, which can include four nitrogen-containing heterocycles linked together. In some embodiments, the nitrogen-containing heterocycles are selected from the group consisting of pyrrole and pyrroline, and are linked together by methylene groups (i.e., =CH- groups) to form a tetrapyrrole. The nitrogen-containing macrocyclic compound can include, for example, porphyrin compounds (four pyrrole groups linked together by methylene groups), chlorin compounds (three pyrrole groups and one pyrroline group linked together by methylene groups), bacteriochlorophyll compounds or isobacteriochlorophyll compounds (two pyrrole groups and two pyrroline groups linked together by methylene groups), or porphyrinoids having a heteroaromatic ring core or a partially aromatic ring core (such as texaphrin or subporphyrin), or functional equivalents thereof (i.e., ring nuclei that are not aromatic throughout the circumference of the ring), or polypyrrole compounds (such as boron-dipyrromethene). It should also be understood that the term "nitrogen-containing macrocyclic compound" can be one of the compounds listed herein or can be a combination of the compounds listed herein. Thus, the nitrogen-containing macrocyclic compound can include porphyrins, reduced porphyrins, or mixtures thereof. Such nitrogen-containing macrocyclic compounds can also be referred to as "polypyrrole macrocyclic compounds" (e.g., tetrapyrrole macrocyclic compounds).

[0120] It should be understood that as used herein, the term "reduced porphyrin" refers to the group consisting of chlorins, bacteriochlorophylls, isobacteriochlorophylls, and other types of reduced porphyrins (such as corrins and corphins).

[0121] 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., magnesium porphyrin, magnesium chlorophyllin, copper chlorophyllin, iron protoporphyrin IX, etc.). The nitrogen-containing macrocyclic compound can be an extracted naturally occurring compound or a synthetic compound.

[0122] In embodiments where the 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 reactive singlet oxygen species. For example, in the case of chlorins and porphyrins, non-limiting examples of metals that can typically form a type II photosensitizer to generate reactive singlet oxygen species are Mg, Zn, Pd, Sn, Al, Pt, Si, Ge, Ga, and In. Similarly, non-limiting examples of metals known to form a type I photosensitizer when complexed with chlorins and / or porphyrins are Cu, Co, Fe, Ni, and Mn.

[0123] It should be understood that when referring to a metal species without referring to its oxidation state, all suitable oxidation states of the metal species will be considered, as understood by those skilled in the art. In other embodiments, 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 other embodiments, the metal species can be selected from the group consisting of Cu(II), Co(II), Fe(II), and Mn(II). In other embodiments, the metal species can be selected from the group consisting of Co(III), Fe(III), Fe(IV), and Mn(III).

[0124] It should also be understood that the specific metal that may result in the formation of a type II photosensitizer relative to the metal that results in the formation of a type I photosensitizer can vary depending on the type of nitrogen-containing macrocyclic compound to which it binds. It should also be understood that a non-metallized nitrogen-containing macrocyclic compound can be a type I photosensitizer or a type II photosensitizer. For example, both chlorin e6 and protoporphyrin IX are type II photosensitizers.

[0125] It should be understood that the nitrogen-containing macrocyclic compounds used in the methods and compositions of this specification 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 enhanced environmental biodegradability properties compared to other types of nitrogen-containing macrocyclic compounds (such as phthalocyanines).

[0126] The following formulae illustrate several non-limiting examples of nitrogen-containing macrocyclic compounds that can be used in the methods and compositions described herein:

[0127]

[0128]

[0129] Various nitrogen-containing macrocyclic compounds, such as Zn-TPP and Mg-chlorophyllin, can be obtained from chemical suppliers such as Organic Herb Inc., Sigma Aldrich, or Frontier Scientific. In some cases, the nitrogen-containing macrocyclic compounds are not 100% pure and may include other components such as organic acids and carotenoids. In other cases, the nitrogen-containing macrocyclic compounds can have high purity.

[0130] Modified Ce6 photosensitizer

[0131] One of the above compounds, chlorin e6 (Ce6), is a tetrapyrrole with a 20-carbon atom macrocycle, where each pyrrole is connected to two other pyrroles of the macrocycle by a carbon bridge. In the following description of Ce6, the carbons of the macrocycle are numbered 1 to 20. In the chemical structure of Ce6, three groups with carboxylic acids are provided at the C13(COOH), C15(CH2COOH), and C17(CH2CH2COOH) positions.

[0132]

[0133] The photosensitizer compounds of this specification can be based on the above Ce6 scaffold, where at least one of the C13, C15, and C17 carboxylic acids can be functionalized. The modified Ce6 compounds can be metallated or non-metallated. Examples of such modified Ce6, their activities, and methods of manufacture are described in PCT patent application number PCT / CA2020 / 050083, which is incorporated herein by reference in its entirety.

[0134] In some embodiments, the modified Ce6 can be a compound of formula I:

[0135]

[0136] or an agriculturally acceptable salt thereof,

[0137] wherein:

[0138] each Z 1 、Z 2 and Z 3 is independently OR 1 or NR2 R 3 ;

[0139] Each R 1 、R 2 and R 3 is independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl, provided that if Z 1 、Z 2 and Z 3 are each OR 1 , then at least one R 1 is not H, and if Z 1 、Z 2 and Z 3 are each NR 2 R 3 , then at least one R 3 is not H;

[0140] Each R a 、R b 、R c 、R d 、R e and R f is independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0141] is a single bond or a double bond;

[0142] is a single bond or a double bond; and

[0143] M is 2H or a metal species,

[0144] wherein substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl are independently substituted by one or more -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 - )、-NR B -(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)NRB 2- or -C(=NR B )NR B 2-substituted;

[0145] Each X is independently a halogen: F, Cl, Br, or I;

[0146] Each R B is independently H, alkyl, aryl, arylalkyl, heterocycle, alkoxy (such as poly(ethyleneoxy), PEG, or poly(methyleneoxy), capped poly(ethyleneoxy), capped PEG, or capped poly(methyleneoxy)), or a protecting group;

[0147] The capped poly(ethyleneoxy), capped PEG, and capped poly(methyleneoxy) groups are each independently capped with alkyl, aryl, arylalkyl, alkenyl, alkynyl, CO(alkyl), CO(aryl), CO(arylalkyl), CO(alkenyl), or CO(alkynyl);

[0148] Each R C is independently alkyl, aryl, arylalkyl, O(alkyl), O(aryl), O(arylalkyl), or O(trisubstituted silyl);

[0149] Each trisubstituted silyl is independently substituted with three functional groups selected from alkyl, alkenyl, alkynyl, aryl, and arylalkyl; and

[0150] Each Alk is independently alkylene, alkenylene, or alkynylene.

[0151] In some embodiments, the modified Ce6 can be a compound of formula I:

[0152]

[0153] or an agriculturally acceptable salt thereof,

[0154] wherein:

[0155] Z 1 is OR 1 ;

[0156] Z 2 and Z 3 one of which is NR 2 R 3 , NR 2 -(CH2) n -NR 4 R 5 , NR 2 -(CH2) n -N + R 4 R 5 R6 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(R 7 )3、NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 、OR 3 、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 -SR8 、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; and

[0157] Z 2 and Z 3 The other one is OR 12 ;

[0158] or

[0159] Z 2 It 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 R10 、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 、OR 3 、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; and

[0160] Z 3 =Z 2 ;

[0161] Each R 1 、R 2 、R 4 、R 6 、R 8 、R 9 、R 10 、R 11 and R 12 is independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl or -(CH2) q -(CH2CH2O) m -R 13 ;

[0162] Each R 3 and R 5 is independently alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl or -(CH2) q -(CH2CH2O) m -R 13 ;

[0163] R 7 is alkyl, O(alkyl) or O(trisubstituted silyl);

[0164] R 13 is H, alkyl, substituted alkyl, aryl, substituted aryl, CO(alkyl) or CO(substituted alkyl), alkenyl, substituted alkenyl, CO(alkenyl) or CO(substituted alkenyl), alkynyl, substituted alkynyl, CO(alkynyl) or CO(substituted alkynyl);

[0165] W + is an agriculturally acceptable cation;

[0166] Y - is an agriculturally acceptable anion;

[0167] n is an integer selected from 1 to 16;

[0168] p is an integer selected from 1 to 16;

[0169] q is an integer selected from 0 to 16;

[0170] m is an integer selected from 1 to 100;

[0171] Each R a 、R b 、R c 、R d 、R e and R f is independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0172] is a single bond or a double bond;

[0173] is a single bond or a double bond; and

[0174] M is 2H or a metal substance,

[0175] wherein each substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl is independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0176] In some embodiments, the modified Ce6 can be a compound of formula I:

[0177]

[0178] or an agriculturally acceptable salt thereof,

[0179] wherein:

[0180] Z 1 is OR 1 ;

[0181] Z 2 and Z 3 One of them 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、NR2 -(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)[[ID=...]] 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 + R9 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

[0182] Z 2 and Z 3 The other one is OR 12 ;

[0183] or

[0184] Z 2 It 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(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 -NR 4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3; and

[0185] Z 3 =Z 2 ;

[0186] Each R1 , R 2 and R 12 are independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0187] R 3 is alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0188] Each R 4 , R 6 , R 8 , R 9 , R 10 and R 11 are independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl or –(CH2) q -(CH2CH2O) m -R 13 ;

[0189] R 5 is alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl or -(CH2) q -(CH2CH2O) m -R 13 ;

[0190] R 7 is alkyl, O(alkyl) or O(trisubstituted silyl);

[0191] 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);

[0192] W + is an agriculturally acceptable cation;

[0193] Y - is an agriculturally acceptable anion;

[0194] n is an integer selected from 1 to 16;

[0195] p is an integer selected from 1 to 16;

[0196] m is an integer selected from 1 to 100;

[0197] q is an integer selected from 0 to 16;

[0198] Each R a , Rb , R c , R d , R e and R f are independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0199] is a single bond or a double bond;

[0200] is a single bond or a double bond; and

[0201] M is 2H or a metal substance,

[0202] wherein each of the substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl is independently substituted by one or more of F, Cl, Br, I, CN and N3.

[0203] In some embodiments, is a single bond; and is a double bond.

[0204] When is a single bond, the two asymmetric carbons in the modified Ce6 can independently be of any configuration (R) or (S). For example, the two asymmetric carbons in the modified Ce6 can each be of the (S) configuration.

[0205] In some embodiments, each R a , R b , R c , R d , R e and R f are independently alkyl or alkenyl. For example but not limited to, R a , R c , R e and R f can be methyl; R b can be vinyl; and R d can be ethyl.

[0206] In some embodiments, M is 2H. In some embodiments, M is a metallic 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 metallic species is mentioned without mentioning its degree of oxidation, all suitable oxidation states of the metallic species are considered, as understood by those skilled in the art. In other embodiments, M is a metallic 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 other embodiments, M is a metallic species selected from the group consisting of Cu (II), Co (II), Fe (II) and Mn (II).

[0207] 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. 3 and R 5 are independently alkyl or substituted alkyl. 13 is H, alkyl, substituted alkyl, CO(alkyl) or CO(substituted alkyl).

[0208] In some embodiments, the compound is selected such that at least one of the following is true: R 1 It's H, R 2 It's H, R 3 is an alkyl group, R 4 is H or alkyl, R 5 is an alkyl group, R 6 is an alkyl group, R 7 is O(trisubstituted silyl), R 8 Yes - (CH2) q -(CH2CH2O) m -R 13 , R 9 is an alkyl group, R 10 is an alkyl group, R 11 is an alkyl group, R 12 is H and R 13 is H, alkyl, alkenyl, CO(alkyl) or CO(alkenyl).

[0209] 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 ion, bromide ion, phosphate ion, dimethyl phosphate ion, methyl sulfate ion, ethyl sulfate ion, acetate ion, and lactate ion.

[0210] 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 is an integer that can be 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 implementations, q = 1. In other embodiments, q = 0.

[0211] 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 9 R10 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 、OR 3 、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 + 或O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3且Z 3is OR 12 or Z 3 = Z 2 .

[0212] 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 .

[0213] In some embodiments, Z 3 is OR 12 . For example, Z 3 can be OH. In other embodiments, Z 3 = Z 2 .

[0214] In some embodiments, the modified Ce6 can be a compound of formula I-B1:

[0215]

[0216] or an agriculturally acceptable salt thereof,

[0217] wherein:

[0218] Z 1 is OR 1 ;

[0219] R 2 is H, an alkyl group or a substituted alkyl group;

[0220] R 3 is an alkyl group or a substituted alkyl group;

[0221] Z 3 is OR 12 or Z 3 =NR 2 R 3 ;

[0222] Each R 1 and R 12 are independently H, an alkyl group or a substituted alkyl group;

[0223] Each R a 、R b 、R c 、R d 、R e and R f are independently H, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group or a substituted alkynyl group; and

[0224] M is 2H or a metal substance,

[0225] wherein the substituted alkyl group, the substituted alkenyl group and the substituted alkynyl group are independently substituted by one or more of F, Cl, Br, I, CN and N3.

[0226] In some embodiments, R 1 is H, R 2 is H and / or R 3 is an alkyl group. R 3 can be, for example, a (C1-C 12 ) alkyl group, a (C1-C8) alkyl group or a (C1-C4) alkyl group. In some embodiments, Z 3 is OR 12 and R 12 can be H. In other embodiments, Z 3 =NR 2 R 3 .

[0227] In some embodiments, the modified Ce6 can be a compound of formula I-B2:

[0228]

[0229] or an agriculturally acceptable salt thereof,

[0230] wherein:

[0231] Z 1 is OR 1;

[0232] R 5 is an alkyl group, a substituted alkyl group or -(CH2) p -NR 9 R 10 ;

[0233] Each R 2 、R 4 、R 9 and R 10 is independently H, an alkyl group or a substituted alkyl group;

[0234] n is an integer selected from 1 to 16;

[0235] p is an integer selected from 1 to 16;

[0236] Z 3 is OR 12 or Z 3 =NR 2 -(CH2) n -NR 4 R 5 ;

[0237] Each R 1 and R 12 is independently H, an alkyl group or a substituted alkyl group;

[0238] Each R a 、R b 、R c 、R d 、R e and R f is independently H, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group or a substituted alkynyl group; and

[0239] M is 2H or a metal substance,

[0240] wherein the substituted alkyl group, the substituted alkenyl group and the substituted alkynyl group are independently substituted by one or more of F, Cl, Br, I, hydroxyl group, CN and N3.

[0241] In some embodiments, R 1 is H, R 2 is H and / or R 4 is H or an alkyl group. In some embodiments, R 4 is H and R 5 is an alkyl group. In some embodiments, R 4 and R 5 are alkyl groups. R 4 and / or R 5 can be, for example, (C1-C 12An alkyl group, a (C1-C8) alkyl group, or a (C1-C4) alkyl group. In some embodiments, R 5 is -(CH2) p -NR 9 R 10 。In some embodiments, R 9 and R 10 are alkyl groups, or R 9 is H and R 10 is an alkyl group. R 9 and / or R 10 can be, for example, a (C1-C 12 ) alkyl group, a (C1-C8) alkyl group, or a (C1-C4) alkyl group. 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.

[0242] In some embodiments, the modified Ce6 can be a compound of Formula I-B3:

[0243]

[0244] or an agriculturally acceptable salt thereof,

[0245] wherein:

[0246] Z 1 is OR 1 ;

[0247] Z 4 is Si(R 7 )3 or SR 8 ;

[0248] Z 3 is OR 12 or Z 3 =NR 2 -(CH2) n -Z 4 ;

[0249] Each R 1 、R 2 and R 12 is independently H, an alkyl group, or a substituted alkyl group;

[0250] R 7 is an alkyl group, O(alkyl), or O(trisubstituted silyl);

[0251] R 8 is H, an alkyl group, a substituted alkyl group, or -(CH2CH2O) m -R 13 ;

[0252] R 13is 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);

[0253] n is an integer selected from 1 to 16;

[0254] m is an integer selected from 1 to 100;

[0255] 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; and

[0256] M is 2H or a metal substance,

[0257] wherein the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0258] 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), wherein alkyl 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, Z 3 is OR 12 . In other embodiments, Z 3 =NR 2 -(CH2) n -Z 4 .

[0259] In some embodiments, the modified Ce6 can be a compound of formula I-B4a:

[0260]

[0261] or an agriculturally acceptable salt thereof,

[0262] wherein:

[0263] Z 1 is OR 1 ;

[0264] Z 3 is OR 12 or Z 3 = NR2-(CH2) n -O(PO3H) - W + ;

[0265] Each R 1 、R 2 and R 12 is independently H, alkyl or substituted alkyl;

[0266] n is an integer selected from 1 to 16;

[0267] W + is an agriculturally acceptable cation;

[0268] 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; and

[0269] M is 2H or a metal substance,

[0270] wherein the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0271] 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. 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 + 。

[0272] In some embodiments, the modified Ce6 can be a compound of formula I-B4c:

[0273]

[0274] or an agriculturally acceptable salt thereof,

[0275] Wherein:

[0276] Z 1 is OR 1 ;

[0277] Z 3 is OR 12 or Z 3 = NR2-(CH2) n -NR 4 R 5 R 6+ Y - ;

[0278] Each R 1 、R 2 and R 12 is independently H, alkyl or substituted alkyl;

[0279] Each R 4 、R 5 and R 6 is independently alkyl or substituted alkyl;

[0280] n is an integer selected from 1 to 16;

[0281] Y - is an agriculturally acceptable anion;

[0282] 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; and

[0283] M is 2H or a metal substance,

[0284] wherein the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0285] 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 . Y- is selected from the group consisting of chloride ion, bromide ion, phosphate ion, dimethyl phosphate ion, methyl sulfate ion, ethyl sulfate ion, acetate ion and lactate ion. In some embodiments, Z 3 is OR 12 . In other embodiments, Z 3 = NR2-(CH2) n -NR 4 R 5 R 6+ Y - .

[0286] In some embodiments, the modified Ce6 can be a compound of Formula I-C:

[0287]

[0288] or an agriculturally acceptable salt thereof,

[0289] wherein:

[0290] Z 1 is OR 1 ;

[0291] Z 3 = OR 12 and m is an integer selected from 1 to 100; or

[0292] Z 3 = O(CH2CH2O) m -R 13 and m is an integer selected from 5 to 100;

[0293] Each R 1 and R 12 is independently H, alkyl or substituted alkyl;

[0294] 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);

[0295] 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;

[0296] is a single bond or a double bond;

[0297] is a single bond or a double bond; and

[0298] M is 2H or a metal substance,

[0299] wherein the substituted alkyl, substituted alkenyl, and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN, and N3.

[0300] 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 . In some embodiments, R 13 is H, alkyl, alkenyl, CO(alkyl), or CO(alkenyl).

[0301] Non-limiting examples of the modified Ce6 photosensitizer include:

[0302]

[0303]

[0304]

[0305]

[0306] or an agriculturally acceptable salt thereof.

[0307] Modified PpIX photosensitizer

[0308] One of the above compounds, protoporphyrin IX (PP IX), is one of the most common porphyrins in nature. PP IX is a dark pigment that exists in nature in the form of its iron complex. When complexed with ferrous ions, this molecule is called heme. Other iron complexes have also been synthesized, such as complexes with Fe(III) or Fe(IV). PP IX is a large planar tetrapyrrole with a 20-carbon atom macrocycle, and each pyrrole is connected to two other pyrroles of the macrocycle through a carbon bridge. In the following description of PP IX, the carbons of the macrocycle are numbered 1 to 20. In the chemical structure of PP IX, two moieties with carboxylic acids are provided at the C13(CH2CH2COOH) and C17(CH2CH2COOH) positions.

[0309]

[0310] The photosensitizer compounds of the present specification can be based on the above-mentioned PpIX scaffold, in which at least one of the C13 and C17 carboxylic acids can be functionalized. The modified PpIX compounds can be metallized or non-metallized. Examples of such modified PpIX, their activities, and methods of manufacture are described in PCT patent application number PCT / CA2020 / 050197, which is hereby incorporated by reference in its entirety.

[0311] In some embodiments, the modified PpIX can be a compound of Formula II:

[0312]

[0313] or an agriculturally acceptable salt thereof, wherein:

[0314] Z 1 and Z 2 are each independently OR 1 or NR 2 R 3 ;

[0315] Each R 1 、R 2 and R 3 is independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl, wherein:

[0316] If Z 1 and Z 2 are both OR 1 , then at least one R 1 is not H,

[0317] If Z 1 and Z 2 are both NR 2 R 3 , then at least one R 3 is not H, and

[0318] If one of Z 1 and Z 2 is OR 1 and the other of Z 1 and Z 2 is NR 2 R 3 , then at least one of R 1 and R 3 is not H;

[0319] Each R a 、R b 、R c, R d , R e and R f are independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0320] is a single bond or a double bond;

[0321] is a single bond or a double bond; and

[0322] M is 2H or a metal substance,

[0323] wherein the substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl are independently substituted by one or more -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 - ), -NR B -(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 B is substituted;

[0324] Each X is independently a halogen: F, Cl, Br or I;

[0325] Each R B is independently H, alkyl, aryl, arylalkyl, heterocycle, alkoxy (such as poly(ethyleneoxy), PEG or poly(methyleneoxy), capped poly(ethyleneoxy), capped PEG or capped poly(methyleneoxy)), or a protecting group;

[0326] The capped poly(ethyleneoxy), capped PEG and capped poly(methyleneoxy) groups are each independently capped with alkyl, aryl, arylalkyl, alkenyl, alkynyl, CO(alkyl), CO(aryl), CO(arylalkyl), CO(alkenyl) or CO(alkynyl);

[0327] Each R Cindependently an alkyl, aryl, arylalkyl, O(alkyl), O(aryl), O(arylalkyl) or O(trisubstituted silyl);

[0328] each trisubstituted silyl is independently substituted by three functional groups selected from alkyl, alkenyl, alkynyl, aryl and arylalkyl; and

[0329] each Alk is independently an alkylene, alkenylene or alkynylene.

[0330] In some embodiments, the compound of formula II is such that:

[0331] Z 1 and Z 2 one of which is OR 1 ; and

[0332] 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 -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 -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 + 或O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3;

[0333] 或

[0334] Z 1 是NR 2 R 3 、NR2 -(CH2) n -NR 4 R 5 、NR 2 -(CH2) n -N + R 4 [[ID=1…… 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(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 -NR 4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3; and

[0335] Z 2 =Z 1 ;

[0336] Each R 1 and R 2 is independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0337] R 3 is alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0338] 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 ;

[0339] R5 is alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl or -(CH2) q -(CH2CH2O) m -R 13 ;

[0340] R 7 is alkyl, O(alkyl) or O(trisubstituted silyl);

[0341] 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);

[0342] W + is an agriculturally acceptable cation;

[0343] Y - is an agriculturally acceptable anion;

[0344] n is an integer selected from 1 to 16;

[0345] p is an integer selected from 1 to 16;

[0346] m is an integer selected from 1 to 100;

[0347] q is an integer selected from 0 to 16;

[0348] Each R a , R b , R c , R d , R e and R f is independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0349] is a single bond or a double bond;

[0350] is a single bond or a double bond; and

[0351] M is 2H or a metal species,

[0352] wherein each substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl is independently substituted by one or more of OH, F, Cl, Br, I, CN and N3.

[0353] In some embodiments, Z 1 = Z 2 = NR2 R 3 。In other embodiments, 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 。R 3 can be, for example, an alkyl or a substituted alkyl.

[0354] In some embodiments, is a double bond and / or is a double bond. More specifically: In some cases, is a double bond and is a double bond. In other cases, is a double bond and is a single bond. In other cases, is a single bond and is a double bond. In other cases, is a single bond and is a single bond.

[0355] In some embodiments, each R a 、R b 、R c 、R d 、R e and R f is independently an alkyl or an alkenyl. In a non-limiting example, R a 、R c 、R e and R f are methyl, while R b and R d are vinyl.

[0356] In some embodiments, M is 2H. In some embodiments, M is a metal 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 referring to a metal without specifying its oxidation state, all suitable oxidation states of the metal will be considered, as understood by those skilled in the art. In other embodiments, M is 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), and In(III). In other embodiments, M is a metal selected from the group consisting of Cu(II), Co(II), Fe(II), and Mn(II). In other embodiments, M is a metal selected from the group consisting of Cu(II), Co(III), Fe(III), and Mn(III).

[0357] 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).

[0358] 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), R 8 is H or alkyl, R 9 is alkyl, R 10 is alkyl, R 11 is alkyl and R 13 is H, alkyl, alkenyl, CO(alkyl), or CO(alkenyl).

[0359] In some embodiments, W + is selected from the group consisting of sodium, potassium, magnesium, and ammonium cations. In some embodiments, Y -Selected from the group consisting of chloride ions, bromide ions, phosphate ions, dimethyl phosphate ions, methyl sulfate ions, ethyl sulfate ions, acetate ions, and lactate ions.

[0360] 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 is an integer that can be 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. Still with respect to the PEG moiety, q is an integer that can be selected from 0 to 16, or 0 to 8, or 0 to 4, or 0 to 2. In some implementations, q = 1. In other implementations, q = 0.

[0361] 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 、NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、NR2 -(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 -NR 4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3; and Z 2 =Z 1 .

[0362] In some embodiments, Z1 and Z 2 one 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 or NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 ; and Z 1 and Z 2 the other of which 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 -NR4 -(CH2) p -NR 9 R 10 ; and Z 2 =Z 1 .

[0363] 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 of Z 1 and Z 2 is OR 1 .

[0364] 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 or NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 ; and Z 2 = Z 1 .

[0365] In some embodiments, the modified PP IX can be a compound of Formula II-B1:

[0366]

[0367] or an agriculturally acceptable salt thereof.

[0368] In some implementations:

[0369] Z 1 and Z 2 one of which is NR 2 R 3 ; and

[0370] Z 1 and Z 2 the other of which is OR 1 ;

[0371] or

[0372] Z 1 = NR 2 R 3 ; and

[0373] Z 2 = Z 1 ;

[0374] Each R 1 and R 2 is independently H, alkyl or substituted alkyl;

[0375] R 3 is alkyl or substituted alkyl;

[0376] Each R a , R b , R c , R d , R e and R findependently is H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl; and

[0377] M is 2H or a metal substance,

[0378] wherein the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of OH, F, Cl, Br, I, CN and N3.

[0379] 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, one of Z 1 and Z 2 is NR 2 R 3 ; and the other of Z 1 and Z 2 is OR 1 . In other embodiments, Z 1 =NR 2 R 3 ; and Z 2 =Z 1 .

[0380] In some implementations:

[0381] One of Z 1 and Z 2 is NR 2 -(CH2) n -NR 4 R 5 or O-(CH2) n -NR 4 R 5 ; and

[0382] the other of Z 1 and Z 2 is OR 1 ;

[0383] or

[0384] Z 1 =NR 2 -(CH2) n -NR 4 R 5 or O-(CH2) n -NR 4 R 5 ; and

[0385] Z 2 =Z 1 ;

[0386] R 5 is an alkyl, a substituted alkyl or -(CH2) p -NR 9 R 10 ;

[0387] Each R 1 、R 2 、R 4 、R 9 and R 10 is independently H, an alkyl or a substituted alkyl;

[0388] n is an integer selected from 1 to 16;

[0389] p is an integer selected from 1 to 16;

[0390] Each R a 、R b 、R c 、R d 、R e and R f is independently H, an alkyl, a substituted alkyl, an alkenyl, a substituted alkenyl, an alkynyl or a substituted alkynyl; and

[0391] M is 2H or a metal substance,

[0392] wherein the substituted alkyl, the substituted alkenyl and the substituted alkynyl are independently substituted by one or more of OH, F, Cl, Br, I, CN and N3.

[0393] In some embodiments, R 1 is H, R 2 is H and / or R 4 is H or an alkyl. In some embodiments, R 4 is H and R 5 is an alkyl. In some embodiments, R 4 and R 5 are alkyls. R 4 and / or R 5 can each independently be, for example, a (C1-C 12 ) alkyl, a (C1-C8) alkyl or a (C1-C4) alkyl. In some embodiments, R 5 is -(CH2) p -NR 9 R 10 . In some embodiments, R 9 and R 10 are alkyls, or R 9 is H and R10 is an alkyl group. R 9 and / or R 10 may each independently be, for example, a (C1-C 12 ) alkyl group, a (C1-C8) alkyl group or a (C1-C4) alkyl group.

[0394] 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.

[0395] In some embodiments, one of Z 1 and Z 2 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 .

[0396] In some implementations:

[0397] One of Z 1 and Z 2 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

[0398] the other of Z 1 and Z 2 is OR 1 ;

[0399] or

[0400] Z 1 =NR 2 -(CH2) n -Si(R7 ) 3, O-(CH2) n -Si(R 7 )3, NR 2 -(CH2) n -SR 8 or O-(CH2) n -SR 8 ; and

[0401] Z 2 = Z 1 ;

[0402] Each R 1 and R 2 is independently H, alkyl or substituted alkyl;

[0403] R 7 is alkyl, O(alkyl) or O(trisubstituted silyl);

[0404] R 8 is H, alkyl, substituted alkyl or -(CH2) q -(CH2CH2O) m -R 13 ;

[0405] 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);

[0406] n is an integer selected from 1 to 16;

[0407] m is an integer selected from 1 to 100;

[0408] q is an integer selected from 0 to 16;

[0409] 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; and

[0410] M is 2H or a metal substance,

[0411] wherein the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of OH, F, Cl, Br, I, CN and N3.

[0412] In some embodiments, R 1 is H and / or R2 is H. In some embodiments, R 7 is alkyl, O(alkyl), or O(trisubstituted silyl). The alkyl of 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 8 is -(CH2) q -(CH2CH2O) m -R 13 . 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 implementations, q = 1. In other implementations, q = 0.

[0413] In some embodiments, one of Z 1 and Z 2 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 .

[0414] In some implementations:

[0415] Z 1and Z 2 One of them 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

[0416] Z 1 and Z 2 The other one is OR 1 ;

[0417] or

[0418] 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

[0419] Z 2 =Z 1 ;

[0420] Each R 1 and R 2 is independently H, alkyl or substituted alkyl;

[0421] n is an integer selected from 1 to 16;

[0422] W + is an agriculturally acceptable cation;

[0423] 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; and

[0424] M is 2H or a metal substance,

[0425] Wherein the substituted alkyl, substituted alkenyl, and substituted alkynyl are each independently substituted by one or more of OH, F, Cl, Br, I, CN, and N3.

[0426] In some embodiments, R 1 is H and / or R 2 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.

[0427] In some embodiments, one of Z 1 and Z 2 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 .

[0428] In some implementations:

[0429] 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

[0430] Z 1 and Z 2 Another one in 1 ; [[ID=1 Twelve]]

[0431] or

[0432] 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

[0433] Z 2 = Z 1 ;

[0434] Each R 1 and R 2 is independently H, alkyl or substituted alkyl;

[0435] Each R 4 、R 5 and R 6 is independently alkyl or substituted alkyl;

[0436] n is an integer selected from 1 to 16;

[0437] Y - is an agriculturally acceptable anion;

[0438] 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; and

[0439] M is 2H or a metal substance,

[0440] wherein the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of OH, F, Cl, Br, I, CN and N3.

[0441] In some embodiments, R 1 is H and / or R 2It 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. 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 ion, bromide ion, phosphate ion, dimethyl phosphate ion, methyl sulfate ion, ethyl sulfate ion, acetate ion and lactate ion.

[0442] 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 .

[0443] In some implementations:

[0444] One of Z 1 and Z 2 is NR 2 -(CH2CH2O) m -R 13 or O-(CH2CH2O) m -R 13 ; and

[0445] One of Z 1 and Z2 Another one in it is OR 1 ;

[0446] or

[0447] Z 1 = NR 2 -(CH2CH2O) m -R 13 or O-(CH2CH2O) m -R 13 ; and

[0448] Z 2 = Z 1 ;

[0449] Each R 1 and R 2 is independently H, alkyl or substituted alkyl;

[0450] 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);

[0451] m is an integer selected from 1 to 100;

[0452] 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; and

[0453] M is 2H or a metal substance,

[0454] wherein the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of OH, F, Cl, Br, I, CN and N3.

[0455] 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, R 13 is H, alkyl, alkenyl, CO(alkyl) or CO(alkenyl).

[0456] In some embodiments, one of Z 1 and Z 2 is NR 2-(CH2CH2O) m -R 13 or O-(CH2CH2O) m -R 13 ; and Z 1 and Z 2 one of the other 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 .

[0457] In some implementations:

[0458] Z 1 and Z 2 one of them is a natural amino acid attached to the compound through the amino group bonded to its α-carbon; and

[0459] Z 1 and Z 2 the other is OR 1 ;

[0460] or

[0461] Z 1 is a natural amino acid attached to the compound through the amino group bonded to its α-carbon; and

[0462] Z 2 =Z 1 ;

[0463] Each R 1 and R 2 is independently H, alkyl or substituted alkyl;

[0464] 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; and

[0465] M is 2H or a metal substance,

[0466] wherein the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of OH, F, Cl, Br, I, CN and N3.

[0467] In some embodiments, Z1 and Z 2 One of them is a natural amino acid attached to the compound through an amino group bonded to its α-carbon; and Z 1 and Z 2 The other one is OR 1 .

[0468] In other embodiments, Z 1 is a natural amino acid attached to the compound through an amino group bonded to its α-carbon; and Z 2 =Z 1 .

[0469] In some embodiments, Z 1 is one of the natural amino acids and Z 2 is OH; 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 .

[0470] In some embodiments, Z 1 is glycine or L-valine and Z 2 is OH; 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 .

[0471] Non-limiting examples of the modified PP IX photosensitizer include:

[0472]

[0473]

[0474]

[0475]

[0476]

[0477] or an agriculturally acceptable salt thereof.

[0478] Film-forming agent

[0479] The film-forming composition of the present specification includes a film-forming agent that can form a substantially oxygen-impermeable film when at least a part of the liquid carrier is removed after being applied to a plant. The film-forming agent can be any compound capable of forming a film that is oxygen-impermeable in the dry or non-hydrated state and becomes permeable to oxygen in the 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., photosensitizer, antioxidant, and any other components of the composition). The film formed by the film-forming agent can slow down the degradation of the photosensitizer by restricting the contact between the photosensitizer and oxygen molecules from the ambient air. In some implementations, the film can slow down the degradation of the photosensitizer by slowing down the transport of oxygen when in the dry or non-hydrated state, and can allow oxygen molecules to pass through at a higher rate when in the hydrated state.

[0480] 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 polymer that forms a hydrogel, and in this case, the film formed 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.

[0481] 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, hydroxypropyl cellulose polyvinylpyrrolidone, guar gum, nanocellulose, soy protein isolate, whey protein, collagen, starch, hydroxypropylated high amylose corn starch, high amylose corn starch, xylan, polyvinylidene chloride, polyvinyl alcohol (PVOH), ethylene vinyl alcohol (EVA), polyvinyl alcohol copolymers, and combinations thereof.

[0482] In some embodiments, the film-forming agent is a film-forming protein that forms a film that is substantially oxygen-impermeable when in the non-hydrated state. Non-limiting examples of such film-forming agents include soy protein isolate, whey protein, and collagen.

[0483] In some embodiments, the film-forming agent is a film-forming polysaccharide that forms a film that is substantially oxygen-impermeable when in the non-hydrated state. Non-limiting examples of such film-forming agents include guar gum and carboxymethyl cellulose.

[0484] In some embodiments, the film-forming agent is polyvinyl alcohol. The term "polyvinyl alcohol" is intended to cover thermoplastic polymers derived from polyvinyl acetate by partial or complete hydroxylation (or hydrolysis). The degree of hydrolysis generally determines the physical, chemical, and mechanical properties of polyvinyl alcohol. The degree of hydrolysis also generally affects the maximum water absorption. Polyvinyl alcohol is very hydrophilic and thus has good solubility in water. Films made of polyvinyl alcohol tend to have heat-sealing properties, oxygen, nitrogen, and carbon dioxide barrier properties, and good adhesion to other hydrophilic surfaces when in a non-hydrated state. Polyvinyl alcohol films are biocompatible, biodegradable, and non-phytotoxic, making them very suitable for application to plants.

[0485] Polyvinyl alcohol can have an average molecular weight of about 10 kDa to about 200 kDa or about 50 kDa to about 100 kDa. For example, polyvinyl alcohol can have an average molecular weight of about 13 kDa to about 23 kDa, or about 31 kDa to about 50 kDa, or about 89 kDa to about 98 kDa, or about 146 kDa to about 186 kDa. Polyvinyl alcohol can have a degree of hydrolysis equal to or greater than 70%, or equal to or greater than 80%, or equal to or greater than 87%, or between 87% and 89%, or equal to or greater than 89%, or between 89% and 99%, or equal to or greater than 99%.

[0486] In some embodiments, polyvinyl alcohol has an average molecular weight of about 50 kDa to about 100 kDa and a degree of hydrolysis equal to or greater than 99%. In some embodiments, polyvinyl alcohol has an average molecular weight of about 13 kDa to about 23 kDa and a degree of hydrolysis equal to or greater than 98%. In some embodiments, 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, polyvinyl alcohol has an average molecular weight of about 89 kDa to about 98 kDa and a degree of hydrolysis equal to or greater than 99%. In some embodiments, polyvinyl alcohol has an average molecular weight of about 146 kDa to about 186 kDa and a degree of hydrolysis equal to or greater than 99%. In some embodiments, 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, 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, polyvinyl alcohol has an average molecular weight of about 146 kDa to about 186 kDa and a degree of hydrolysis of 87% to 89%.

[0487] In some embodiments, polyvinyl alcohol can be selected from the group consisting of Kuraray Poval TM 、Kuraray Exceval TM 、Sekisui Selvol TMa group consisting of the same and their combinations.

[0488] When the film-forming agent includes a film-forming polymer, the film-forming polymer can be formulated with or without a plasticizer. It should be understood that a plasticizer is an additive that increases the plasticity of a material. Plasticizers are generally liquids or solids with low volatility. Plasticizers generally reduce the attraction between polymer chains to make the polymer chains more flexible. It should be understood that those skilled in the art will know what types of plasticizers can be used with any given film-forming polymer. For example but not limited to, 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.

[0489] Antioxidant

[0490] The film-forming composition of the present specification may include antioxidants that can be included in the film formed from the film-forming agent. Antioxidants are more reactive to ROS than photosensitizers when in solution, in a dispersion, in a hydrogel-like environment, and / or in a hydrated film. The function of the antioxidant is to slow down the degradation of the photosensitizer in solution before film formation and / or when the film-forming composition is applied to a plant and the film is in a hydrated state. In some cases, when the film is in a dry or non-hydrated state, the antioxidant does not slow down the degradation of the photosensitizer.

[0491] Antioxidants can be selected from the group consisting of phenolic antioxidants, chain-terminating antioxidants, physical quenchers of singlet oxygen, flavonoids, tocopherols, carotenoids, and antioxidant enzymes.

[0492] In some embodiments, the antioxidants are 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, tert-butyl-hydroxyquinone, butylated hydroxytoluene, butylated hydroxyanisole, α-tocopherol, D-α-tocopherol polyethylene glycol succinate, retinyl palmitate, β-carotene, isoascorbic acid, sodium isoascorbate, sodium ascorbate, ascorbic acid, glutathione, superoxide dismutase, catalase, sodium azide, 1,4-diazabicyclo[2.2.2]octane (DABCO), and their combinations.

[0493] In some embodiments, the antioxidant is a phenolic antioxidant, which may be selected from the group consisting of gallate compounds or their derivatives, vanillin compounds or their derivatives, tannin compounds or their derivatives, lignin compounds or their derivatives, and combinations thereof. Without limitation, the phenolic antioxidant may 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.

[0494] In some embodiments, the antioxidant is a chain-terminating antioxidant, which may be selected from the group consisting of thiol-containing compounds (e.g., glutathione), ascorbic acid or its derivatives, and combinations thereof.

[0495] In some embodiments, the antioxidant is a physical quencher of singlet oxygen, which may be selected from the group consisting of sodium azide, 1,4-diazabicyclo[2.2.2]octane (DABCO), and combinations thereof.

[0496] In some embodiments, the antioxidant is a flavonoid, such as an anthocyanin compound or its derivative.

[0497] In some embodiments, the antioxidant is a tocopherol, which may be selected from the group consisting of vitamin E (α-tocopherol) or its derivatives (e.g., vitamin E TPGS (D-α-tocopheryl polyethylene glycol succinate)).

[0498] In some embodiments, the antioxidant is a carotenoid, which may be selected from the group consisting of β-carotene, lutein, and combinations thereof.

[0499] In some embodiments, the antioxidant is an antioxidant enzyme, which may be selected from the group consisting of catalase, superoxide dismutase, and combinations thereof.

[0500] Chelating agent

[0501] In some embodiments, the compositions of the present specification may include a chelating agent (also referred to herein as a permeabilizing agent). In some cases, the photosensitizer compound reacts to light by generating ROS, and the chelating agent can increase the overall effect of inhibiting the growth of microbial pathogens, 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 chelation bonds with one or more metals or ions.

[0502] In some embodiments, the chelating agent can include at least one carboxyl group, at least one hydroxyl group, at least one phenolic 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 aminopolycarboxylic acid or an agriculturally acceptable salt thereof. For example, the aminopolycarboxylic acid can include two amino groups and two alkyl carboxyl groups bonded to each amino group. The alkyl carboxyl group can be a methyl carboxyl group.

[0503] 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 an agriculturally acceptable salt thereof.

[0504] In some embodiments, the compositions of the present specification include one or more aminopolycarboxylic acid chelating agents. Examples of aminopolycarboxylic acid chelating agents include but are not limited to ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), and ethylenediaminedisuccinic acid (EDDS), cyclohexanediaminetetraacetic acid (CDTA), N-(2-hydroxyethyl)ethylenediaminetriacetic acid (EDTA-OH), ethylene glycol ether diamine tetraacetic acid (GEDTA), alaninediacetic acid (ADA), alkyl ethylenediaminetriacetic acid (e.g., lauroyl ethylenediaminetriacetic 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), diethylenetriamine pentamine ethylene phosphonic acid (DTPMP), diglycolic acid, pyridine dicarboxylic acid (DPA), ethanolamine diacetic acid, ethanol diglycine (EDG), ethylenediamine diglutamic acid (EDDG), ethylenediamine bis(hydroxyphenylacetic acid (EDDHA), ethylenediamine dipropionic acid (EDDP), ethylenediamine disuccinate (EDDS), ethylenediamine monosuccinate (EDMS), ethylenediaminetetraacetic acid (EDTA), ethylenediamine tetrapropionic acid (EDTP), and ethylene glycol aminoethyl ester tetraacetic acid (EGTA) and agriculturally acceptable salts thereof (e.g., sodium salts, calcium salts, and / or potassium salts).

[0505] A non-limiting example of the chelating agent is ethylenediaminetetraacetic acid (EDTA) or an agriculturally acceptable salt thereof. The aminocarboxylate can be, for example, a sodium salt or a calcium salt.

[0506] Another non-limiting example of the chelating agent is polyaspartic acid or an agriculturally acceptable salt thereof (i.e., polyaspartate), such as sodium polyaspartate. The molecular weight of the polyaspartate can be, for example, between 2,000 and 3,000.

[0507] Thus, the chelating agent can be a polymeric compound, which can include aspartate units, carboxyl groups, and other features present in the polyaspartate. The polyaspartate can be a copolymer having α and β linkages, which can be in various proportions (e.g., 30% α, 70% β, randomly distributed along the polymer chain). A non-limiting example of sodium polyaspartate is DS 100.

[0508] 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 an agriculturally acceptable salt thereof. The chelating agent can be metallized or non-metallized. In some embodiments, IDS can be used as the tetrasodium salt of IDS (e.g., tetrasodium iminodisuccinate), which can be CX100. In some embodiments, EDDS can be used as the trisodium salt of EDDS. In some embodiments, GLDA can be used as the tetrasodium salt of GLDA.

[0509] In some embodiments, the chelating agent can include one or more amino acid chelating agents. Examples of amino acid chelating agents include, but are not limited to, alanine, arginine, asparagine, aspartic acid, glutamic acid, glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, proline, serine, threonine, tyrosine, valine, or salts thereof (e.g., sodium salts, calcium salts, and / or potassium salts) and combinations thereof.

[0510] 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, but are not limited to, oxalic acid, succinic acid, pyruvic acid, malic acid, malonic acid, salicylic acid, and anthranilic acid, and salts thereof (e.g., sodium salts, calcium salts, and / or potassium salts).

[0511] In some embodiments, the chelating agent can include one or more hydroxycarboxylic acid chelating agents. Examples of hydroxycarboxylic acid chelating agents include, but are not limited to, malic acid, citric acid, glycolic acid, heptonic acid, tartaric acid, and salts thereof (e.g., sodium salts, calcium salts, and / or potassium salts).

[0512] It should be understood that one or more chelating agents can be provided in the form of free acids, agriculturally acceptable salts, or 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 other embodiments, when there is more than one chelating agent, at least one chelating agent is applied as a free acid and at least one chelating agent is applied as a salt.

[0513] Liquid carrier

[0514] The film-forming composition of the present specification includes a liquid carrier, which can be present in an amount between 5% by weight and 99.9% by weight based on the weight of the film-forming composition to be applied to the plant. In some embodiments, the liquid carrier can be an aqueous carrier.

[0515] It should be understood that as used herein, the term "liquid carrier" refers to a liquid that can dissolve and / or disperse the components of the combinations and compositions of the present specification. In some cases, the liquid carrier can include water. In other cases, the liquid carrier can be water-free. In some embodiments, the liquid carrier can include partially or fully water-soluble organic solvents such as methanol, ethanol, propanol, or butanol, or polyols such as diols (e.g., glycerol, propylene glycol, polypropylene glycol). In some embodiments, the liquid carrier includes non-toxic and biodegradable compounds capable of dissolving and / or dispersing the components of the combinations and compositions described herein.

[0516] It should be understood that the term "aqueous carrier" means a composition comprising greater than or equal to 50% by weight of water and optionally one or more water-soluble compounds and / or water-insoluble solvents, which can form an emulsion with water and / or can be dispersed in water. The aqueous carrier is capable of dissolving and / or dispersing the film-forming agent, photosensitizer, 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 oxygen-impermeable and includes the photosensitizer and other components.

[0517] 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, based on the total amount of the aqueous carrier, the aqueous carrier includes equal to or greater than 80% by weight of water, or equal to or greater than 90% by weight of water, or equal to or greater than 95% by weight of water, or equal to or greater than 99% by weight of water. In some cases and depending on the components of the film-forming composition, the use of water-soluble compounds can help dissolve or disperse the photosensitizer compound in the aqueous carrier.

[0518] In some embodiments, the aqueous carrier can include water-insoluble compounds, such as oils. The oils can be dispersed in water or can form an oil-in-water emulsion. The oils can be selected from the group consisting of mineral oils (e.g., paraffin oil), vegetable oils, essential oils, and mixtures thereof. In some cases and depending on the components of the film-forming composition, the use of oils can help dissolve or disperse the photosensitizer compound in the aqueous carrier. In other embodiments, the aqueous carrier does not contain oil.

[0519] 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, rapeseed oil, soybean oil, canola oil, sunflower oil, safflower oil, peanut oil, cottonseed oil, palm oil, rice bran oil, or mixtures thereof. Non-limiting examples of mineral oils include paraffin oil, branched paraffin oil, naphthenic oil, aromatic oil, or mixtures thereof.

[0520] Non-limiting examples of paraffin oil include various grades of poly-α-olefins (PAO). For example, paraffin oil can include HT60 TM 、HT100 TM 、High Flash Jet、LSRD TM and N65DW TM 。Paraffin oil can include paraffins having from about 12 to about 50 carbon atoms, or from about 16 to 35 carbon atoms. In some cases, the paraffin can have an average carbon atom number of 23. In some embodiments, the oil can have a paraffin content of at least 80 wt%, or at least 90 wt%, or at least 99 wt%.

[0521] 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 embodiments, the oil-in-water emulsion is prepared by a process including mixing the oil, water, and any other components with the oil and applying shear until an emulsion is obtained.

[0522] It should be understood that the liquid carrier generally allows for obtaining a stable solution, suspension, and / or emulsion of the components of the film-forming composition.

[0523] Additives and Adjuvants

[0524] In some embodiments, the compositions of the present specification may include one or more agriculturally suitable adjuvants. Each of the one or more agriculturally suitable adjuvants may independently be 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 herbicide safeners). Exemplary adjuvants are provided in Hazen, J.L., Weed Technology 14:773-784 (2000), which is incorporated herein by reference in its entirety.

[0525] In some embodiments, the composition may also include a surfactant (also referred to as an emulsifier or dispersant). The surfactant may 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 may be sorbitan fatty acid ester. The surfactant may include plant-derived glycosides such as saponins. The surfactant may be present as an adjuvant to assist in covering the plant leaves. The surfactant may be an acceptable polysorbate-type surfactant (e.g., Tween 80), a nonionic surfactant blend (e.g., Altox TM 3273) or another suitable surfactant. In other embodiments, the liquid carrier is surfactant-free.

[0526] In some embodiments, the poly(ethylene glycol) may include a poly(ethylene glycol) of the formula R 15 -O-(CH2CH2O) f -R 16 wherein: each R 15 and R 16 is independently H, alkyl, substituted alkyl, aryl, substituted aryl, CO(alkyl), or CO(substituted alkyl); and f is an integer selected from 1 to 100; wherein the substituted alkyl is independently substituted with one or more F, Cl, Br, I, hydroxyl, alkenyl, CN, and N3.

[0527] 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 having polyvalent cations such as calcium, magnesium, and aluminum), alkynediols, fluorinated aliphatic esters, perfluoroalkylphosphonic acids or their salts, and perfluoroalkylphosphinic acids or their salts.

[0528] In some embodiments, the composition can include an antifreeze agent. Non-limiting examples of antifreeze agents include diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, 1,3-propanediol, 1,2-propanediol, and polyethylene glycol.

[0529] In some embodiments, the composition can include a UV protectant, which can stabilize at least some components of the composition against the effects of UV light. Non-limiting examples of UV protectants include hindered amine light stabilizers, titanium dioxide, zinc oxide, nano-titanium dioxide, nano-zinc oxide, benzophenone, or combinations thereof.

[0530] Film-forming compositions and combinations

[0531] Single composition

[0532] In some embodiments, the film-forming agent, photosensitizer, antioxidant, and / or other optional components can be formulated as a single composition. In some cases, all components can be contained within a storage package or container suitable for applying the composition to a plant. In some cases, the single composition can be a concentrate that is diluted (e.g., with water or another liquid carrier) before being applied to the plant.

[0533] In some embodiments, based on the total weight of the film-forming composition, the film-forming composition can include 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 of an antioxidant. In some embodiments, based on the total weight of the film-forming composition, the film-forming composition can include 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 about 0.25 wt%, or about 0.1 wt% to about 0.2 wt% of an antioxidant.

[0534] In some embodiments, based on the total weight of the film-forming composition, the film-forming composition may comprise 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 of a film-forming agent. In some embodiments, based on the total weight of the film-forming composition, the film-forming composition may comprise from about 0.01 wt% to about 20 wt%, or from about 0.01 wt% to about 10 wt%, or from about 0.05 wt% to about 5 wt%, or from about 0.1 wt% to about 1 wt%, or from about 0.1 wt% to about 0.5 wt% of a film-forming agent.

[0535] In some embodiments, based on the total weight of the film-forming composition, the film-forming composition may comprise 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 of a photosensitizer. In some embodiments, based on the total weight of the film-forming composition, the film-forming composition may comprise from about 0.01 wt% to about 10 wt%, or from about 0.01 wt% to about 2 wt%, or from about 0.05 wt% to about 2 wt%, or from about 0.1 wt% to about 1 wt%, or from about 0.1 wt% to about 0.5 wt% of a photosensitizer.

[0536] In some embodiments, based on the total weight of the film-forming composition, the liquid carrier is present in an amount between 5 wt% and 99.9 wt%. The liquid carrier is capable of dissolving 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 oxygen-impermeable and includes the photosensitizer and other components.

[0537] In some embodiments, the film-forming agent and the antioxidant may be present in the composition in 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.

[0538] In some embodiments, the film-forming agent and the photosensitizer may be present in the composition in 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.

[0539] In some embodiments, the photosensitizer and the film-forming agent may be present in the composition in 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.

[0540] Multi-packaged preparation

[0541] 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 a multi-pack formulation. In some embodiments, the components of the film-forming composition that will ultimately be present on the plant can be separately packaged and / or stored before being applied to the plant, and the combination can be assembled before being applied to the plant. In other embodiments, the components of the film-forming composition that will ultimately be present on the plant can be separately packaged and / or stored before being applied 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.

[0542] For example, the film-forming agent can be separately packaged in a dry state or as a solution and / or dispersion in a liquid carrier, and the photosensitizer and antioxidant can be packaged together in a dry state or as a solution and / or dispersion in a liquid carrier. Any suitable additives and / or adjuvants can be added to one or both packages.

[0543] In some embodiments, the antioxidant and the film-forming agent can be provided in a first package, and the photosensitizer can be provided in a second package. In other embodiments, the antioxidant and the photosensitizer can be provided in a first package, and the film-forming agent can be provided in a second package. In other embodiments, the film-forming agent and the photosensitizer can be provided in a first package, and the antioxidant can be provided in a second package. It should be understood that the liquid carrier can be present in either or both of the first and second packages. When forming the composition, water or an additional liquid carrier can be added when combining the first and second packages.

[0544] In other embodiments, the photosensitizer, the film-forming agent, and the antioxidant can each be provided in a separate package. It should be understood that the liquid carrier can be present in one or all of the individual packages. When forming the composition, water or an additional liquid carrier can be added to one or all of the packages.

[0545] Mode of administration

[0546] The combinations and compositions of the present specification can be applied to plants in various ways. For example but not limited to, the combinations and compositions of the present specification can be applied by spraying, misting, sprinkling, pouring, dipping, or any other suitable method. The combinations and compositions can be applied to the leaves, roots, and / or stems of the plant.

[0547] 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 in an indoor location, where they are exposed to artificial light.

[0548] In some cases, the combinations and compositions of the present specification can be directly applied to plants as a preventive measure before the plants are infested with pests. In other cases, the combinations and compositions of the present specification can be applied when or after the plants are infested with pests.

[0549] Stability of photosensitizers

[0550] Now referring to Figure 1 , and without being bound by theory, shows a schematic diagram of a film obtained from the film-forming combinations or compositions of the present specification. In (a), the film in the non-hydrated state stabilizes the photosensitizer against photo-degradation by minimizing the interaction between the photosensitizer and oxygen. When the film is in the non-hydrated state, due to the oxygen barrier property of the film, the photosensitizer generates fewer reactive oxygen species. In (b), the film in the hydrated state (or the film at high relative humidity) results in oxygen permeation and the generation of reactive oxygen species. Then the reactive oxygen species can protect the plant from various biotic or abiotic stresses. In (c), the antioxidant embedded in the film scavenges the excessive reactive oxygen species in the film to further protect the photosensitizer from photo-degradation when the film is in the hydrated state.

[0551] Thus, the photosensitizer can be protected in two ways: when the film is in the non-hydrated state, by selecting the film-forming material itself such that the film is substantially oxygen-impermeable when in the non-hydrated state; and when the film is in the hydrated state, by selecting the film-forming material with an antioxidant such that the film is oxygen-permeable when in the hydrated state (or when the film is at high relative humidity).

[0552] It should be understood that the meanings of the terms "hydrated state" and "non-hydrated state" depend on the nature of the film-forming agent and the nature of the film obtained from the film-forming agent. In fact, the first film obtained from the first film-forming agent generally has different oxygen barrier properties from the second film obtained from the second film-forming agent. For example, when the relative humidity is below about 50% RH or 60% RH, the film obtained from certain grades of polyvinyl alcohol is generally substantially oxygen-impermeable. Therefore, for a film made of certain grades of polyvinyl alcohol, the statement "the film is in a hydrated state" can mean "the film is in an environment with a relative humidity between 50% RH and 100% RH", or "the film is in an environment with a relative humidity between 60% RH and 100% RH". Similarly, the statement "the film is in a non-hydrated state" can mean "the film is in an environment with a relative humidity below 50% RH" or "the film is in an environment with a relative humidity below 60% RH". It should be 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 specific to that grade. Those skilled in the art know how to measure the oxygen permeability of a given film-forming agent at different relative humidity levels and determine the relative humidity at which each film obtained from a given film-forming agent can be considered to be in a "hydrated state" or a "non-hydrated state". A non-limiting example showing how to measure the effect of moisture content on the structure of polyvinyl alcohol polymers can be found in Journal of Coatings Technology and Research 14, 1345 - 1355, 2017, which is incorporated herein by reference in its entirety.

[0553] It should be understood that, as used herein, the term "substantially oxygen-impermeable" means the ability of a material (e.g., a film) to block or slow down the permeation of oxygen. In the context of this specification, a film can be considered "substantially oxygen-impermeable" when the permeation rate of oxygen through the film is blocked or reduced. In the case where the film includes a photosensitizer, when the oxygen-mediated photodegradation rate of the photosensitizer present in the film is lower than the oxygen-mediated photodegradation rate of the same photosensitizer in the absence of the film, under other identical conditions (temperature, %RH, pressure, etc.), the film can be considered "substantially oxygen-impermeable". Alternatively, when the oxygen-mediated photodegradation rate of the photosensitizer present in the film is lower than the oxygen-mediated photodegradation rate of the same photosensitizer present in a film known to be highly permeable to oxygen under other identical conditions (temperature, %RH, pressure, etc.) (e.g., a silicone-based hydrogel), the film can be considered "substantially oxygen-impermeable". It should be understood that the term "impermeable" does not imply that a "substantially oxygen-impermeable" film is above or below any specific impermeability standard measurement value.

[0554] It should also be understood that the transition between a "hydrated state" and a "non-hydrated state" of the film, and vice versa, can be a sudden or continuous transition. For example, when a composition comprising a film (e.g., in a hydrated state) is applied to a plant and allowed to air dry under ambient conditions, the film can gradually become less hydrated (i.e., gradually change from a hydrated state to a non-hydrated state), and the oxygen impermeability of the film can gradually increase until an equilibrium value is reached.

[0555] When a photosensitizer, film-forming agent, antioxidant, liquid carrier, and any other components are mixed to form a film-forming composition, the film-forming agent is typically dissolved or dispersed in the liquid carrier. In such cases, the antioxidant can protect the photosensitizer from photo-degradation 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, e.g., by air drying. As a portion of the liquid carrier dries, the film-forming agent begins to form a film comprising all of the components of the film-forming composition. The antioxidant can protect the photosensitizer from photo-degradation before the formed film is obtained. When a film is formed on the plant and at least partially removes the liquid carrier, an oxygen barrier is obtained as the film forms, and the photosensitizer is protected from photo-degradation when the contact between the photosensitizer and oxygen is restricted.

[0556] Method for improving plant health

[0557] In some embodiments, a method for promoting plant health is provided. The method comprises applying to the plant a combination or composition comprising: a photosensitizer that generates reactive oxygen species in the presence of light and oxygen, the photosensitizer 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, film-forming agent, and optional antioxidant are dissolved and / or dispersed.

[0558] The method can further comprise removing at least a portion of the liquid carrier from the applied composition (i.e., after application to the plant) to form a substantially oxygen-impermeable film. Removing at least a portion of the liquid carrier from the applied composition can be carried out by any known technique. For example, exposing the plant to a low humidity environment, exposing the plant to heat and / or exposing the plant to air, an inert gas, or a nitrogen stream without damaging the plant. In some embodiments, the plant is air dried under ambient conditions. For example, removing at least a portion of the liquid carrier from the applied composition can include allowing 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, when the liquid carrier (e.g., an aqueous carrier) dries after the composition is applied to the plant, the film-forming agent forms a substantially oxygen-impermeable film.

[0559] Microbial pathogens

[0560] Microbial pathogens to which a composition comprising a photosensitizer compound can be applied include fungal and bacterial pathogens. In this case, the composition can be referred to as an "antimicrobial composition".

[0561] 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 can generally infect turfgrass. Other fungal pathogens in the genera Alternaria, Botrytis, or Sclerotinia can also receive the application of the antimicrobial composition. The antimicrobial composition can be applied to plants 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.

[0562] 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. Erwinia amylovara causes fire blight in various plants, including pears, apples, and other Rosaceae crops. The antimicrobial composition can be applied to plants 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.

[0563] It is also noted that depending on the type of plant and pathogen and the state of microbial infection, the antimicrobial compositions described herein can have various inhibitory effects on microbial pathogens. While it is described herein that the antimicrobial composition can inhibit the growth of microbial pathogens on plants, this expression should not be limiting, but should be understood to include inhibiting microbial pathogens, preventing microbial pathogens, killing microbial pathogens, or generally increasing toxicity to microbial pathogens.

[0564] Abiotic stress

[0565] As described above, in some embodiments, the photosensitizer compounds and compositions of the present specification can be used to increase the tolerance of plants to one or more abiotic stresses, such as photooxidative conditions, drought (water deficiency), overwatering (flooding and submergence), extreme temperatures (low temperature, freezing, and heat), extreme light levels (high and low), radiation (UV-B and UV-A), salinity due to excess Na + ( ) alkalinity, 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 stressors.

[0566] Cold tolerance

[0567] When the abiotic stress is cold stress, applying a photosensitizer compound alone or in combination with additives such as oils, surfactants, and / or chelating agents can improve the cold tolerance of plants. That is, the application of the photosensitizer compound can allow the plants to withstand temperature conditions colder than those typically experienced by the plants under optimal or natural growth conditions. Various types of cold stress are possible, such as unexpected frosts (e.g., early autumn frost when healthy crops, fruits, grains, seeds, or leaves are still present on the plants, or late spring frost that occurs after plant growth has started in the spring), colder than average growing seasons, colder than natural winter conditions, minimal winter snow cover, ice accumulation, etc.

[0568] It should be noted that what constitutes cold stress conditions for one plant may not be cold stress conditions for another plant. Referring to the USDA zone map, the cold stress conditions for plants in zone 9 can actually be the natural growth conditions for plants in zone 8. Similarly, the depth of snow cover required for the survival of one type of plant may not be necessary for a second type of plant. Therefore, it should be understood that various types of cold stress are possible depending on the type of plant being discussed.

[0569] The photosensitizer compounds, compositions, or combinations described herein can be used to protect plants (including woody plants, non-woody plants, and turf grasses) from frost damage. The frost can be an early frost, such as before harvest, after harvest, and before dormancy. The frost can be a late frost, such as after budding. Cold damage can also be winter kill induced by winter temperatures, which can lead to the loss of living shoots or twigs and cause plant death. Plants treated with the photosensitizer compounds, compositions, or combinations described herein can be frost or cold-sensitive plants because they are naturally vulnerable to economically or aesthetically significant amounts of frost, freezing, or cold damage or injury.

[0570] Increased resistance to cold stress can be demonstrated by delaying the onset of dormancy. Plant dormancy may be triggered by a drop in temperature, such as the onset of cold stress. By increasing the plant's resistance to cold stress, the plant's dormancy may be delayed until triggered by a further drop in temperature.

[0571] The photosensitizer compounds, compositions, or combinations described herein can be used regularly (e.g., at intervals of 2 or 3 weeks, starting in the spring when dormancy is broken) and / or by applying one or more treatments (e.g., 2 times in the fall) to provide a response that reduces or delays the dormancy period of certain plants.

[0572] As used herein, the term "reduced dormancy period" refers to a plant having a reduced dormancy period or an extended growing season relative to a control (e.g., an untreated plant).

[0573] In some embodiments, the harvesting step can be carried out one week, one month, two months or longer after the last application of the photosensitizer compound, composition or combination described herein, wherein the active agent remains effective during the intervening period in reducing the effects of cold stress on the plant.

[0574] In some cases, resistance to cold stress includes resistance to early or late frost or winter damage. In some cases, the photosensitizer compounds, compositions or combinations described herein can be used to protect early growth from cold during temperature fluctuations (e.g., in early spring). In some cases, the photosensitizer compounds, compositions or combinations described herein can be used to protect plants from cold during cold months (e.g., in winter).

[0575] In some cases, the photosensitizer compounds, compositions or combinations described herein can be applied by soil drenching and / or foliar application (e.g., spraying until runoff) starting at or before exposure to low temperatures (e.g., in the fall when the tree has fully healthy and vigorous leaves). In some cases, the photosensitizer compounds, compositions or combinations described herein can be applied by soil drenching and / or foliar application (e.g., spraying until runoff) in late fall and winter (e.g., for warm climates). In some cases, the photosensitizer compounds, compositions or combinations described herein can be applied by soil drenching in late fall followed by foliar application (e.g., spraying until runoff) in winter to achieve maximum cold hardiness.

[0576] In some cases, 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 carried out in the spring and / or growing season to increase resistance to subsequent cold stress conditions.

[0577] Heat tolerance

[0578] When the abiotic stress is heat stress, application of the photosensitizer compounds, compositions or combinations described herein can increase tolerance to high temperatures during the growing season. That is, application of the photosensitizer compounds, compositions or combinations described herein can allow the plant to withstand temperature conditions that are hotter than those typically experienced by the plant under optimal or natural growth conditions. Heat stress can have various causes, such as lack of shade for plants that normally require shaded growth conditions, or higher than normal soil and air temperatures.

[0579] It should be noted that what constitutes a heat stress condition for one plant may not be a heat stress condition for another plant.

[0580] Photooxidation resistance

[0581] When the abiotic stress is photooxidative stress, the application of the photosensitizer compounds, compositions or combinations described herein can increase the tolerance to stressful light conditions during the period of increased reactive oxygen species generation. That is, the application of the photosensitizer compounds, compositions or combinations described herein can allow plants to withstand higher light exposure conditions (e.g., ultraviolet irradiation conditions) than those typically experienced by plants under optimal or natural growth conditions. Photooxidative stress can have various causes, such as strong light conditions or certain types of light that induce free radical formation.

[0582] It should be noted that what constitutes photooxidative stress conditions for one plant may not be photooxidative stress conditions for another plant.

[0583] Shade resistance

[0584] Shade stress or "low light (LL) stress" can be a problem affecting plant growth and quality. When the abiotic stress is shade stress, the application of the photosensitizer compounds, compositions or combinations described herein can increase the shade resistance of plants. That is, the application of the photosensitizer compounds, compositions or combinations described herein can allow plants to withstand shade conditions that are typically required for partial or full sun exposure for plants under their optimal or natural growth conditions. Various types of shade stress are possible, such as extended cloudy weather, overgrowth of neighboring plants or trees that cast shadows on the plant, or lack of a sunny planting location.

[0585] Shading can be a periodic problem. For example, in certain months of the year, structures located near the plant may cast shadows on the plant, causing shade stress. As the Earth moves during the course of a year, the structure may no longer cast a shadow on the plant in the following months, and then this situation can repeat in 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 shade stress period and can also be applied during the shade stress period. Damage to the plant that would normally result from shade stress can be prevented or reduced.

[0586] For many types of plants, shade conditions are not considered abiotic stress conditions because some plants require shade as part of their optimal growth conditions. It should also be noted that what constitutes shade stress conditions for one plant may not be shade stress conditions for another plant.

[0587] Drought tolerance

[0588] Drought can be defined as a period without rainfall or irrigation sufficient to deplete soil moisture and damage plants. Drought stress occurs when the water loss of a plant exceeds the ability of the plant roots to absorb water and / or when the water content of the plant is reduced enough to interfere with normal plant processes. The severity of the impact of drought conditions can vary among plants because the water requirements of plants can vary according to plant type, plant phenological stage, plant age, root depth, soil quality, etc.

[0589] The photosensitizer compounds, compositions or combinations described herein can be applied to plants before the onset of drought and / or during drought. Applying the photosensitizer compounds, compositions or combinations described herein can increase the resistance of plants to drought stress. Increasing resistance can include maintaining or increasing the quality of the plant compared to untreated plants subjected to the same drought stress. Increasing resistance can include reducing the degradation of plant quality compared to untreated plants subjected to the same drought stress. If a plant does not receive sufficient rainfall or irrigation, the resulting drought stress can reduce plant growth more than all other combinations of environmental stresses.

[0590] It should also be noted that what constitutes drought stress conditions for one plant may not be drought stress conditions for another plant.

[0591] Prevention of salt damage

[0592] Salts can occur naturally in the growth environment of plants. Salinity stress refers to the osmotic force exerted on plants when they are growing in saline soils or under other overly saline conditions. For example, plants growing near a saline body of water may be exposed to salts present in the air 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 may transfer and / or leach into the soil of nearby growing plants. This increased salt content in the plant growth environment can cause salinity stress, which can damage the plants.

[0593] Applying the photosensitizer compounds, compositions or combinations described herein to plants can increase the resistance of plants to salinity stress and prevent or reduce the deterioration of plant quality that would occur if untreated. The combination can be applied before or during salinity stress.

[0594] It should also be noted that what constitutes salinity stress conditions for one plant may not be salinity stress conditions for another plant.

[0595] Transplant shock resistance

[0596] Plants that are subjected to transplantation from one growing environment to another, such as from a flower pot to a flower bed or garden, may undergo transplant shock stress due to exposure to new environmental conditions such as wind, direct sunlight, or new soil conditions. Applying the photosensitizer compounds, compositions, or combinations described herein to the roots of plants can reduce the impact of transplantation on the plants. In some cases, the developmental retardation of plant growth and / or the development of transplanted plants can be reduced or prevented by applying the photosensitizer compounds, compositions, or combinations described herein.

[0597] It should be noted that what constitutes transplant shock stress conditions for one plant may not be transplant shock stress conditions for another plant.

[0598] Water tolerance or waterlogging resistance

[0599] Although healthy growth and development of plants require a certain volume of water, exposing plants to an excessive volume of water ("water stress") can damage the plants. Applying the photosensitizer compounds, compositions, or combinations described herein to plants before the onset of excessive water conditions can increase the resistance of the plants to water stress. The photosensitizer compounds, compositions, or combinations described herein can be applied during water stress; however, dilution of the photosensitizer compounds, compositions, or combinations described herein can occur due to the excessive water. Therefore, pretreatment some time before the period of excessive water can be more effective.

[0600] It should be noted that what constitutes excessive water stress conditions for one plant may not be excessive water stress conditions for another plant.

[0601] Insecticidal activity

[0602] In some embodiments, the compounds and combinations of the present specification can be used to protect plants from insect plant pests. It should be understood that the term "insect plant pest" or "insect pest" as used herein refers to insects and / or their larvae that are known or likely to cause damage to plants. In some embodiments, the compounds and combinations of the present specification can induce light-induced death in insect pests.

[0603] In some embodiments, the insect pests are selected from Hemiptera (aphid group, whitefly group, Lepidoptera, mealybug, stink bug), Coleoptera (beetle group), Lepidoptera (butterfly, moth group), Diptera (fly group), Thysanoptera (thrips group), Orthoptera (grasshopper group, locust group), Hymenoptera (wasp group, ant group), Blattodea (cockroach and termite group), and mite pests (spider mite).

[0604] Non-limiting examples of insect pests include: larvae of Lepidoptera such as cutworms (e.g., beet armyworm (Spodoptera exigua)), sugar moths, loopers (e.g., cabbage looper (Trichoplusia ni)) and heliothines of the family Noctuidae (e.g., fall armyworm (Spodoptera fugiperda J.E. Smith), beet armyworm (Spodoptera exigua Hubner), black cutworm (Agrotis ipsilon Hufnagel) and tobacco budworm (Heliothis virescens Fabricius)); borers, case-bearers, webworms, coneworms, cabbageworms and leaf feeders such as those of the family Pyralidae (e.g., European corn borer (Ostrinia nubilalis Hubner), navel orangeworm (Amyelois transitella Walker), sod webworm (Crambus caliginosellus Clemens) and beet webworm (Pyralidae: Crambinae)), leafrollers of the family Tortricidae, aphids, seed bugs and fruit bugs (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruit moth (Grapholita molesta Busck) and many other economically important Lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders) and gypsy moth (Lymantria dispar Linnaeus));Leaf-eating larvae and adults of Coleoptera, including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., the boll weevil (Anthonomus grandis Boheman)), the rice water weevil (Lissorhoptrus oryzophilus Kuschel), the granary weevil (Sitophilus granarius Linnaeus), the rice weevil (Sitophilus oryzae Linnaeus), the bluegrass weevil (Listronotus maculicollis Dietz), the meadow weevil (Sphenophorus parvulus Gyllenhal), the hunting billbug (Sphenophorus venatus vestitus), the Denver billbug (Sphenophorus cicatristriatus Fahraeus), flea beetles, cucumber beetles, rootworms, leaf beetles, the Colorado potato beetle (Leptinotarsa decemlineata), and leaf miners, the western corn rootworm (Diabrotica virgifera virgifera LeConte); chafers and other beetles from the family Scarabaeidae (e.g., the Japanese beetle (Popillia japonica Newman)), the Oriental beetle (Anomala orientalis Waterhouse), the northern masked chafer (Cyclocephala borealis Arrow), the southern masked chafer (Cyclocephala immaculate Olivier), the black turfgrass ataenius (Ataenius spretulus Haldeman), the green June beetle (Cotinis nitida Linnaeus), the Asiatic garden beetle (Maladera castanea Arrow), the May / June beetles (Phyllophaga spp.), and the European chafer (Rhizotrogus majalis Razoumowsky)); the red larder beetle from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae; flour beetles from the family Tenebrionidae;Adults and nymphs of Orthoptera, including grasshoppers, locusts and crickets (e.g., migratory locusts (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas)), American grasshoppers (e.g., Schistocerca americana Drury), desert locusts (Schistocerca gregaria Forskal), migratory locusts (Locusta migratoria Linnaeus), bush crickets (Zonocerus spp.); adults and larvae of Diptera, including leaf miners, midges, fruit flies (Tephritidae), fruit flies (e.g., Oscinella frit Linnaeus), soil maggots; adults and nymphs of Hemiptera and Homoptera, such as plant bugs from Miridae, leafhoppers (e.g., Empoasca spp.) from Cicadellidae; planthoppers (e.g., Peregrinus maidis) from Fulgoroidae and Delphacidae; treehoppers from Membracidae; wheat bugs (e.g., Blissus leucopterus hirtus Montandon and Blissus insularis Barber) and other seed bugs from Lygaeidae; froghoppers from Cercopidae; squash bugs from Coreidae; red bugs and cotton stainers from Pyrrhocoridae; mealybugs (e.g., Planicoccus citri Risso) from Pseudococcidae, cicadas from Cicadidae; psyllids (e.g., Citrus psyllid Diaphorina citri) from Psyllidae, whiteflies (Bemisia argentifolii) from Aleyrodidae;Aphids from the family Aphididae, such as Aphis gossypii, Acyrthisiphon pisum Harris, Aphis craccivora Koch, Aphis fabae Scopoli, Aphis gossypii Glover (melon aphid or cotton aphid), Aphis pomi De Geer, Aphis spiraecola Patc, Aulacorthum solani Kaltenbach, Chaetosiphon fragaefolii Cockerell, Diuraphis noxia Kurdjumov / Mordvilko, Dysaphis plantaginea Paaserini, Eriosoma lanigerum Hausmann, Hyalopterus pruni Geoffroy, Lipaphis erysimi Kaltenbach, Metopolophium dirrhodum Walker, Macrosipum euphorbiae Thomas, Myzus persicae Sulzer (peach potato and green peach aphid), Nasonovia ribisnigri Mosley, root aphids and gall aphids, Rhopalosiphum maidis Fitch, Rhopalosiphum padi Linnaeus, Schizaphis graminum Rondani, Sitobion avenae Fabricius, Therioaphis maculata Buckton, Toxoptera aurantii Boyer de Fonscolombe, Toxoptera citricida Kirkaldy, and Myzus persicae; Phylloxera from the family Phylloxeridae; soft scale insects from the family Pseudococcidae; scales from the families Coccidae, Diaspididae, and Margarodidae;Tingidae lace bugs; Pentatomidae stink bugs; adult and immature Thysanoptera, including Thrips tabaci Lindeman, Frankliniella spp., and other leaf-feeding thrips. Agricultural pests also include invertebrate arthropods such as mites from the family Tetranychidae: Tetranychus spp. (e.g., Tetranychus urticae Koch), Brevipalpus spp. from the family Tenuipalpidae (e.g., Brevipalpus lewisi McGregor); rust and bud mites and other leaf-feeding mites from the family Eriophyidae. Economically important agricultural pest nematodes (e.g., Meloidogyne spp. root-knot nematodes, Pratylenchus spp. root-lesion nematodes, and Trichodorus spp. stubby-root nematodes), and members of the classes Nematoda, Cestoda, Trematoda, and Acanthocephala from the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida.

[0605] Plant type

[0606] The photosensitizer compounds and compositions of the present invention can be used for various types of plants. The plants can be non-woody crop plants, woody plants, or turfgrass. The plants can be selected from the group consisting of crop plants, fruit plants, vegetable plants, legume plants, cereal plants, forage plants, oilseed plants, field plants, garden plants, greenhouse plants, potted plants, flower plants, turf plants, turfgrass, fruit trees such as fruit trees, and other plants that may be affected by microbial pathogens and / or one or more abiotic stresses. In the absence or presence of light, some of the compounds of the present specification may exhibit a certain degree of toxicity to a variety of harmful plant pests.

[0607] In some embodiments, the plant is a crop plant selected from the group consisting of sugarcane, wheat, rice, corn (maize), potato, beet, barley, sweet potato, cassava, soybean, tomato, and legumes (beans and peas).

[0608] In other embodiments, the plant is a tree selected from the group consisting of deciduous trees and evergreen trees. Examples of trees include, but are not limited to, maple trees, fruit trees such as citrus trees, apple trees, and pear trees, oak trees, ash trees, pine trees, and spruce trees.

[0609] In other embodiments, the plant is a shrub.

[0610] In other embodiments, the plant is a fruit or nut plant. Non-limiting examples of such plants include: acerola cherry (Barbados cherry), sugar apple, star fruit, rambutan tree, apricot tree, apricot, cherry, nectarine, peach, pistachio, apple, avocado, banana, plantain, fig, grape, mango, olive, papaya, pear, pineapple, plum, strawberry, grapefruit, lemon, lime, orange (e.g., navel orange and Valencia orange), bellflower, citrus, orange tree, and plants from the group of berry and small fruit plants.

[0611] In other embodiments, the plant is a vegetable plant. Non-limiting examples of such plants include: asparagus, bean, beet, broccoli, Chinese kale, cabbage, brussels sprout, cauliflower, Chinese cabbage (e.g., pak choi and mapa), Chinese mustard (leaf mustard), cavolo nero, kale, kohlrabi, kale spinach, komatsuna, mustard leaf, spinach, rape, celery, zucchini, winter melon, citron melon, cucumber, gherkin, hyotan, cucuzza, loofah, okra, muskmelon, bitter gourd, balsam pear, Chinese cucumber, true cantaloupe, honeydew melon, casaba melon, crenshaw melon, golden pershaw melon, honeydew, honey galls, mango, Persian melon, pumpkin, bush pumpkin, winter squash, watermelon, taro (dasheen), eggplant, ginger, ginseng, herbs and spices (e.g., curly basil, lemon balm, cilantro, Mexican oregano, mint), Japanese radish (daikon), lettuce, okra, pepper, potato, radish, sweet potato, Chinese artichoke (Japanese artichoke), corn, and tomato.

[0612] In other embodiments, 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 plants and foliage plants, including roses and other flowering shrubs, foliage plants and bedding plants, fruit-bearing trees such as apple trees, cherry trees, peach trees, and pear trees, fruitless trees, shade trees, ornamental trees, and shrubs (e.g., conifers, deciduous trees, and broadleaf trees, evergreen trees, and woody ornamental plants).

[0613] In some embodiments, the plant is a potted plant. Non-limiting examples of such plants include: chrysanthemum, Dieffenbachia, Dracaena, fern, Gardenia, Geranium, Crassula, palm plant, Philodendron, and Schefflera.

[0614] In some embodiments, the plant is a plant grown in a greenhouse. Non-limiting examples of such plants include: Pogostemon cablin, Euphorbia milii, Dieffenbachia spp., Cornus spp., Dracaena spp., ferns, Ficus spp., Ilex spp., Eustoma spp., Magnolia spp., Orchidaceae spp., palm plants, Petunia hybrida, Euphorbia pulcherrima, Schefflera spp., Helianthus spp., Aglaonema spp., Aster spp., Rhododendron spp., Begonia spp., Amethystanthus spp., Camellia japonica, Dianthus caryophyllus, Celosia cristata, Chrysanthemum spp., Lamiaceae spp., Cosmos bipinnatus, Lagerstroemia indica, Senecio cineraria, Lilium longiflorum, Fuchsia spp., Gardenia jasminoides, Gerbera jamesonii, Helichrysum bracteatum, Hibiscus spp., Spiraea spp., Impatiens spp., Crassula arborescens, Calendula officinalis, Impatiens hawkeri, Nicotiana tabacum, Philodendron spp., Portulaca oleracea, Rieger begonias, Antirrhinum majus, and Zinnia elegans.

[0615] 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 an adult plant, and the composition is applied directly to the adult plant. It should be understood that an adult plant is a plant that has grown beyond the seed or seedling stage.

[0616] In some embodiments, the composition of the present specification is applied to non-renewable parts of the plant. It should be understood that the term "non-renewable parts of the plant" refers to parts of the plant from which the entire plant cannot grow or regenerate when the part of the plant is placed in a growth medium. In some embodiments, the composition of the present specification can be applied to non-renewable parts of an adult plant (e.g., the leaves of an adult plant).

[0617] Synergy of the combination

[0618] In some cases, the combination can exhibit a synergistic response to inhibit the growth of microbial pathogens in plants. It should be understood that, as used herein, the terms "synergy" or "synergistic" refer to the interaction of two or more components of a combination (or composition) such that their combined effect is greater than the sum of their individual effects. In the context of the present specification, this can include the action of two or more of a photosensitizer, a film-forming agent, an antioxidant, an oil, and a chelating agent. In some cases, a nitrogen-containing macrocyclic compound and a film-forming agent can be present in synergistically effective amounts. In some cases, a photosensitizer and an antioxidant can be present in synergistically effective amounts. In some cases, a film-forming agent and an antioxidant can be present in synergistically effective amounts. In some cases, a photosensitizer, a film-forming agent, and an antioxidant can be present in synergistically effective amounts.

[0619] In some cases, methods such as those presented by S.R. Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20 - 22 (1967) can be used to evaluate synergy. The expected efficacy E can be expressed as: E = X + Y(100 - X) / 100, where X is the efficacy of the first component of the combination, expressed as % of the untreated control, and Y is the efficacy of the second component of the combination, expressed as % of the untreated control. When the observed efficacy is higher than the expected efficacy, the two components are said to be present in synergistically effective amounts.

[0620] Example

[0621] General procedures and formulations

[0622] Chlorophyllin-PVOH-tannic acid preparation

[0623] The preparation of a formulation showing the photo - stability of a photo - activated photosensitizer is described by the following example method: This example describes the preparation of a formulation of (0.1% magnesium phyllochlorin + 0.5% polyvinyl alcohol (89 kDa; 99% + hydrolyzed, PVOH89 - h) + 0.05% tannic acid). First, a 5 wt% PVOH89 - h solution is prepared by slowly adding 5 g of solid PVOH89 - h to a beaker containing 95 g of deionized water (dH2O) with mixing. The beaker is heated to a temperature of 95 °C and mechanically stirred for 1 hour. The dissolved solution is cooled and transferred to a clean glass bottle for later use. Second, a 1 wt% tannic acid solution is prepared by dissolving 1 g of tannic acid (Sigma - Aldrich, St. Louis, MO) in 99 g of dH2O and can be used without further treatment. Third, a 1 wt% sodium salt stock solution of magnesium phyllochlorin is prepared by adding 1 g of magnesium phyllochlorin to 99 g of dH2O. Into a 10 g glass vial, 1 g of 1% magnesium phyllochlorin is 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 is capped, mixed, and used within 1 week of preparation.

[0624] It should be understood that other (photosensitizer + water - absorbent polymer + optional antioxidant + optional additional components) solutions can be formulated using the above method. The following formulations are prepared using the above method. All percentage values before the components of the formulation represent weight % values based on the total weight of the formulation. The percentage values 99% h, 89% h represent the % hydrolysis of PVOH. MgChln means magnesium pheophorbide e6; AlChln means aluminum pheophorbide e6.

[0625] -0.1% MgChln + 0.05% PVOH (89 kDa 99% h);

[0626] -0.1% MgChln + 0.1% PVOH (89 kDa 99% h);

[0627] -0.1% MgChln + 0.25% PVOH (89 kDa 99% h);

[0628] -0.1% MgChln + 0.5% PVOH (89 kDa 99% h);

[0629] -0.1% MgChln + 0.5% PVOH (89 kDa 99% h) + 0.01% tannic acid;

[0630] -0.1% MgChln + 0.5% PVOH (89 kDa 99% h) + 0.05% tannic acid;

[0631] -0.1% MgChln + 0.5% PVOH (13 kDa 99% h);

[0632] -0.1% MgChln + 0.5% PVOH (31 kDa 99% h);

[0633] -0.1% MgChln + 0.5% PVOH (146 kDa 99% h);

[0634] -0.1% MgChln + 0.5% PVOH (13 kDa 89% h);

[0635] -0.1% MgChln + 0.5% PVOH (31 kDa 89% h);

[0636] -0.1% MgChln + 0.5% PVOH (89 kDa 89% h);

[0637] -0.1% MgChln + 0.5% PVOH (146 kDa 89% h);

[0638] -0.1% MgChln + 0.5% PVOH (13 kDa 99% h) + 0.05% tannic acid;

[0639] -0.1% MgChln + 0.5% PVOH (31 kDa 99% h) + 0.05% tannic acid;

[0640] -0.1% MgChln + 0.5% PVOH (89 kDa 99% h) + 0.05% tannic acid;

[0641] -0.1% MgChln + 0.5% PVOH (146 kDa 99% h) + 0.05% tannic acid;

[0642] -0.1% MgChln + 0.5% PVOH (13 kDa 89% h) + 0.05% tannic acid;

[0643] -0.1% MgChln + 0.5% PVOH (31 kDa 89% h) + 0.05% tannic acid;

[0644] -0.1% MgChln + 0.5% PVOH (89 kDa 89% h) + 0.05% tannic acid;

[0645] -0.1% MgChln + 0.5% PVOH (146 kDa 89% h) + 0.05% tannic acid;

[0646] -0.1% MgChln + 0.5% PVOH (146 kDa 99% h) + 0.05% tannic acid + 0.05% glycerol;

[0647] -0.1% MgChln + 0.5% PVOH (146 kDa 99% h) + 0.05% tannic acid + 0.1% glycerol;

[0648] -0.1% MgChln + 0.5% PVOH (146 kDa 99% h) + 0.05% tannic acid + 0.05% propylene glycol;

[0649] -0.1% MgChln + 0.5% PVOH (146 kDa 99% h) + 0.05% tannic acid + 0.1% propylene glycol;

[0650] -0.03% MgChln + 0.5% PVOH (89 kDa 99% h);

[0651] -0.03% MgChln + 0.1% PVOH (89 kDa 99% h);

[0652] -0.03% MgChln + 0.1% vanillin;

[0653] -0.03% MgChln + 0.5% PVOH (89 kDa 99% h) + 0.1% vanillin;

[0654] -0.03% MgChln + 0.25% PVOH (89 kDa 99% h) + 0.05% tannic acid;

[0655] -0.75% MgChln + 0.5% vanillin;

[0656] -0.1% MgChln + 0.5% PVOH (89 kDa 89% h) + 0.05% tannic acid + 0.05% NaEDTA;

[0657] -0.1% MgChln + 0.5% PVOH (89 kDa 89% h) + 0.05% tannic acid + 0.1% NaEDTA;

[0658] -0.1% MgChln + 0.5% PVOH (89 kDa 89% h) + 0.05% tannic acid + 0.1% Pluronics TM F-127;

[0659] -0.1% MgChln + 0.5% PVOH (89 kDa 89% h) + 0.05% tannic acid + 0.1% Breakthru TM SD260

[0660] -0.1% MgChln + 0.5% PVOH (89 kDa 89% h) + 0.05% tannic acid + 0.1% Xiameter TM OFX-309;

[0661] -0.1% MgChln + 0.5% PVOH (89 kDa 89% h) + 0.05% tannic acid + 0.1% saponin

[0662] -0.1% MgChln + 0.5% PVOH (89 kDa 89% h) + 0.05% tannic acid + 0.1% Morwet TM D-400;

[0663] -0.1% MgChln + 0.5% PVOH (89 kDa 89% h) + 0.05% tannic acid + 0.1% Brij TM O10;

[0664] -0.1% MgChln + 0.5% Galactasol 40HFDS + 0.05% tannic acid;

[0665] -0.1% MgChln + 0.5% carboxymethyl cellulose + 0.05% tannic acid;

[0666] -0.1% MgChln + 0.5% poly(vinyl alcohol-co-ethylene) (27 mol% ethylene) + 0.05% tannic acid;

[0667] -0.1% MgChln + 0.5% Solubon TM PT401 + 0.05% tannic acid;

[0668] - 0.1% Chlorophyll e6 disodium salt + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% tannic acid;

[0669] - 0.1% Chlorophyll e6 dimethylaminoethyl ester + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% tannic acid;

[0670] - 0.1% AlChln + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% tannic acid;

[0671] - 0.1% MgChln + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% gallic acid;

[0672] - 0.1% MgChln + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% propyl gallate;

[0673] - 0.1% MgChln + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% vanillin;

[0674] - 0.1% MgChln + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% vanillyl alcohol; and

[0675] - 0.1% MgChln + 0.25% PVOH (89 kDa, 99% hydrolyzed) + 0.05% Borresperse TM NA.

[0676] Method A: Evaluate the photostability in the unhydrated state (also known as "solid state")

[0677] Pipette 50 μL of each formulation into 12 wells of a 96 - well clear - bottom black microplate (Thomas Scientific, Swedesboro, NJ) and dry for 3 hours at 45 °C using a dehydrator (Gourmia GFD1680) to form a film. At the start of the experiment, place the microplate under a Heliospectra RX30 LED lamp array (Heliospectra, San Raphael, CA). Adjust the LED array so that the microplate receives an average of 1300 μmol / m 2The light intensity of / s. The microplate was tightly covered with aluminum foil and peeled back at selected intervals to irradiate the membrane with light for 0 h, 24 h, 48 h, or 72 h. After the light irradiation was completed, the contents of each well were redissolved with 100 μL of boiling dH2O and mixed until complete rehydration. Absorbance spectral scans were performed on the microplate (350 to 750 nm) using a light absorption plate reader (Spectramax M2E, Molecular Devices, San Jose, CA), and the peak intensity was monitored at 24 h, 48 h, and / or 72 h time points and compared with the corresponding 0 h time point to determine the degree of photodegradation. The percentage of photosensitizer remaining after irradiation was calculated using the following equation:

[0678]

[0679] where Abs t is the absorbance peak of the sample that received an exposure of t hours; Abs0 is the absorbance peak of the sample that did not receive an exposure. All data are presented as mean ± standard deviation.

[0680] Method B: Evaluate the photostability in solution (also known as "liquid state")

[0681] Fifty microliters of each formulation was pipetted into 12 wells of a 96-well clear-bottom black microplate (Thomas Scientific, Swedesboro, NJ), and then 50 μL of dH2O was added. The samples were sealed with a microplate transparent adhesive film to minimize water evaporation. At the start of the experiment, the microplate was placed under a Heliospectra RX30 LED lamp array (Heliospectra, San Rafael, CA). The LED array was adjusted so that the microplate received an average light intensity of 1300 μmol / m 2 / s. The microplate was tightly covered with aluminum foil and peeled back at selected intervals to irradiate the membrane with light for 0 h, 2 h, 4 h, or 6 h. After the light irradiation was completed, the adhesive film was removed and the sample absorbance was measured using a light absorption plate reader (Spectramax M2E, Molecular Devices, San Jose, CA). The samples in each well were redissolved with 100 μL of boiling deionized water (dH2O) and mixed until complete rehydration. Absorbance spectral scans were performed on the microplate (350 to 750 nm), and the peak intensity was monitored at 2 h, 4 h, and 8 h time points and compared with the corresponding 0 h time point to determine the degree of photodegradation. The percentage of photosensitizer remaining after irradiation was calculated using the following equation:

[0682]

[0683] where Abst is the absorbance peak of the sample exposed for t hours; Abs0 is the absorbance peak of the sample not exposed to light. All data are expressed as mean ± standard deviation.

[0684] Example 1

[0685] Several preparations with different PVOH (89 kDa; >99% hydrolysis) were evaluated for content using Method A. The results are summarized in Table 1 below:

[0686] Table 1. Effect of poly(vinyl alcohol) (89 kDa; >99% hydrolysis) (PVOH) on the photostability of MgChln after 72 hours of light irradiation

[0687]

[0688] Example 2

[0689] The solid-state and liquid photostabilities of several preparations with PVOH (146 kDa; >99% hydrolysis) and different antioxidant contents (the phenolic antioxidant tannic acid) were evaluated using Method A and Method B. The results are summarized in Table 2 below.

[0690] Table 2. Effects of poly(vinyl alcohol) (146 kDa; >99% hydrolysis) (PVOH) and the phenolic antioxidant tannic acid on the solid-state and liquid photostabilities of MgChln after 72 hours of simulated sunlight irradiation and 6 hours of irradiation, respectively

[0691]

[0692] Example 3

[0693] The solid-state and liquid photostabilities of several preparations with PVOH of different molecular weights and degrees of hydrolysis were evaluated using Method A and Method B. The results are summarized in Table 3 below.

[0694] Table 3. Effects of the molecular weight, degree of hydrolysis of poly(vinyl alcohol) (PVOH), and the addition amount of the phenolic antioxidant tannic acid on the solid-state and liquid photostabilities of MgChln after 72 hours and 6 hours of simulated sunlight irradiation.

[0695]

[0696] Example 4

[0697] The solid-state and liquid photostabilities of several preparations with PVOH (146 kDa; >99% hydrolysis) and tannic acid with different plasticizer contents were evaluated using Method A and Method B. The results are summarized in Table 4 below.

[0698] Table 4. Effect of polymeric plasticizers on the solid and liquid photostability of magnesium chlorophyllin (Mgchln) in poly(vinyl alcohol) (146 kDa; >99% hydrolyzed) (PVOH) and tannic acid formulations. Solid samples were exposed to simulated sunlight for 72 h, while liquid samples were exposed to simulated light for 6 h.

[0699]

[0700] Commercially available PVOH is usually formulated with plasticizers. This experiment shows that plasticizers do not particularly affect the solid and liquid stability of photosensitizers.

[0701] Example 5

[0702] The control of the fungal phytopathogen Colletotrichum orbiculare ATC 20767 (Cgm) on the host plant Nicotiana benthamiana was evaluated after treatment with a formulation containing magnesium chlorophyllin, sodium salt of a hydrogel polymer, poly(vinyl alcohol) 89 kDa (99%+ hydrolyzed), and the phenolic antioxidant vanillin. The N. benthamiana plants were treated approximately 48 h before 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 24 h, followed by dark incubation until distinct disease symptoms appeared on the water-treated control plants. Once the disease symptoms were distinct, the lesions were counted and the leaf area was measured to determine the number of lesions per square centimeter of leaf area. Four replicate plants were used for each treatment, and the plants were randomized under the light source. Illumination was provided by LED lights emitting approximately 450 μmol / m 2 / s photosynthetically active radiation (PAR). The results are summarized in Table 5.

[0703] Table 5. Effect of poly(vinyl alcohol) (89 kDa; >99% hydrolyzed) (PVOH) and the phenolic antioxidant vanillin on the activity of magnesium chlorophyllin (MgChln) against Cgm in N. benthamiana. The sprayed films were irradiated with fluorescent light for 48 h before inoculation with fungal spores.

[0704] Treated material % Disease inhibition Control 0.0 0.03% MgChln 95.1 0.03% MgChln + 0.5% PVOH 89kda 96.9 0.03% MgChln + 0.1% PVOH 89kda 95.6 0.03% MgChln + 0.1% vanillin 99.2 0.03% MgChln + 0.5% PVOH 89kda + 0.1% vanillin 95.9 0.5% PVOH 89kda -55.8

[0705] Example 6

[0706] The control of the fungal plant pathogen Colletotrichum gloeosporioides ATC 20767 (Cgm) on the host plant Nicotiana benthamiana was evaluated after treatment with a formulation containing magnesium phyllochlorin, sodium salt of a hydrogel polymer, polyvinyl alcohol 89 kDa (99%+ hydrolyzed), and the phenolic antioxidant tannic acid. The N. benthamiana plants were treated approximately 48 hours before inoculation to mimic photodegradation on the leaf surface. Subsequently, a spore suspension of Cgm was applied to the leaves. The plants were then exposed to light for 24 hours, followed by dark incubation until distinct disease symptoms appeared on the water-treated control plants. Once the disease symptoms were distinct, the lesions were counted and the leaf area was measured to determine the number of lesions per square centimeter of leaf area. Four replicate plants were used for each treatment, and the plants were randomized under the light source. Illumination was provided by LED lights emitting approximately 450 μmol / m 2 / s photosynthetically active radiation (PAR). The results are summarized in Table 6.

[0707] Table 6. Effects of polyvinyl alcohol (89 kDa; >99% hydrolyzed) (PVOH) and the phenolic antioxidant tannic acid on the activity of magnesium phyllochlorin (MgChln) against C. gloeosporioides in N. benthamiana.

[0708] Treated material % Inhibition Control 0 0.03% MgChln 76 0.03% MgChln + 0.25% PVOH + 0.05% tannic acid 92

[0709] Example 7

[0710] An experiment on the inhibitory effect of the film-forming composition against the plant pathogen Pseudomonas syringae (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 before inoculation, the N. benthamiana plants at the 5- to 6-leaf stage were chemically treated until a fine spray outflow was delivered using a handheld spray bottle. Plants sprayed with water were used as controls. After treatment, the plants were immediately randomized on the racks and exposed to LED light emitting approximately 450 μmol / m2 / s photosynthetically active radiation (PAR) for 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 and diluted to 1x10^8 CFU / ml, followed by the addition of 0.02% (v / v) Silwet L-77. 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 racks in a growth chamber maintained at 24 °C and exposed to LED light emitting approximately 250 μmol / m 2The combination of the fluorescence of / sPAR and LED light was used for 16 hours of illumination / 8 hours of darkness photoperiod for 7 days. The disease severity of the whole plant was evaluated using a 0 to 100% rating scale. Disease symptoms included yellow lesions, leaf discoloration, leaf deformation, and growth arrest. Each treatment was repeated four times in the experiment.

[0711] Table 7. Effects of polyvinyl alcohol (89 kDa; >99% hydrolyzed) (PVOH) and the phenolic antioxidant vanillin on the enhanced activity of magnesium chlorophyllin (MgChln) against Pseudomonas syringae pv. tabaci in Nicotiana benthamiana.

[0712]

[0713] Example 8

[0714] One milliliter samples of dH2O solutions containing 0.75% MgChln or 0.75% MgChln with 0.5% vanillin were prepared in 1.5 mL centrifuge tubes. These samples were wrapped in aluminum foil and stored in an oven at 54 °C for 2 weeks. After 2 weeks, the samples were removed from the 54 °C oven or -20 °C freezer and analyzed using a UV-visible absorbance microplate reader (Spectramax M2E, Molecular Devices, Sunnyvale, CA). Twelve technical replicates were performed for each sample. The remaining % photosensitizer was determined by calculating the degradation of MgChln due to storage at elevated temperature using the following equation:

[0715]

[0716] where Abs t is the absorbance peak of the sample after incubation at 54 °C for 2 weeks; Abs0 is the absorbance peak of the sample at the start of the experiment without storage at 54 °C. All data are presented as mean ± standard deviation. The results are summarized in Table 8.

[0717] Table 8. Thermal stability of magnesium chlorophyllin (MgChln) in the presence and absence of vanillin (2 weeks at 54 °C).

[0718] Treated material Remaining % photosensitizer 0.75% MgChln 62±7 0.75% MgChln + 0.5% vanillin 87±6

[0719] Example 9

[0720] The solid-state and liquid-state photostabilities of several formulations with PVOH (89 kDa; >99% hydrolyzed) and various antioxidants were evaluated using Method A and Method B. The results are summarized in Table 9 below.

[0721] Table 9. Effects of antioxidants and polyvinyl alcohol (89 kDa; >99% hydrolysis) on the photostability of MgChln formulations in solid and liquid states. Solid-state samples were exposed to simulated sunlight for 72 hours, while liquid samples were exposed to simulated light for 6 hours.

[0722]

[0723] 1 Lignosulfonate

[0724] Example 10

[0725] The solid- and liquid-state photostabilities of several formulations with PVOH (189 kDa; >99% hydrolysis), tannic acid, and various adjuvants were evaluated using Methods A and B. The results are summarized in Table 10 below.

[0726] Table 10. Effects of adjuvants on the solid- and liquid-state photostabilities of magnesium chlorophyllin (Mgchln) in polyvinyl alcohol (89 kDa; >99% hydrolysis) (PVOH) and tannic acid formulations. Solid-state samples were exposed to simulated sunlight for 72 hours, while liquid samples were exposed to simulated light for 6 hours.

[0727]

[0728] 1 Triblock copolymer (EO-PO-EO) (BASF, Germany)

[0729] 2 Trisiloxanyl nonionic surfactant (EVONIK)

[0730] 3 3-(3-Hydroxypropyl)-heptamethyltrisiloxane, ethoxylated, acetate (Dow, USA)

[0731] 4 Alkylnaphthalenesulfonate condensate (Nouryon)

[0732] 5 Polyoxyethylene (10) oleyl ether (Croda, UK)

[0733] Example 11

[0734] The solid- and liquid-state photostabilities of several formulations with various film-forming agents and tannic acid MgChln were evaluated using Methods A and B. The results are summarized in Table 11 below.

[0735] Table 11. Effects of polymer materials and tannic acid on the photostability of MgChln in the solid state. Solid-state samples were exposed to simulated sunlight for 72 hours.

[0736]

[0737] 1 Guar gum (Ashland Inc.)

[0738] 2 Polyvinyl alcohol water-soluble film (Aicello Chemical Co., Ltd.)

[0739] All the film-forming agents tested significantly improved the photostability of the photosensitizer in the solid state. The use of tannic acid and most of the film-forming agents also improved the photostability of the photosensitizer in the liquid state. Treatment with MgChln, poly(vinyl alcohol-co-ethylene), and tannic acid appeared to provide similar liquid photostability (within the error bounds) compared to MgChln alone.

[0740] Example 12

[0741] The solid-state and liquid photostabilities of several formulations of various photosensitizers with PVOH (189 kDa; >99% hydrolysis) and tannic acid were evaluated using Method A and Method B. The results are summarized in Table 12 below.

[0742] Table 12. Effects of polyvinyl alcohol (89 kDa; >99% hydrolysis) (PVOH) and tannic acid on the photostability of various tetrapyrroles in the solid and liquid states. Solid samples were exposed to simulated sunlight for 72 hours, while liquid samples were exposed to simulated light for 6 hours.

[0743]

[0744] Wherein Ce6-mixed-DMAE 15,17 The amide is a mixture of the following two compounds:

[0745]

[0746] At approximately 1.5 (Ce6-mono-DMAE 15 amide): 1 (Ce6-bis-DMAE 15,17 amide) molar ratio.

[0747] Examples 13 to 27 demonstrate 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 from abiotic stress, and / or by exhibiting pesticidal activity. These Ce6 and Pp IX compounds can be used in the film-forming combinations and compositions of this specification.

[0748] Example 13:

[0749] Antifungal activity of the modified Ce6 photosensitizer

[0750] Experiments were conducted to evaluate the antifungal activities of several Ce6 derivatives synthesized herein. The following methods were used and the results are summarized in Tables 13A and 13B.

[0751] Agar protocol: The control of Sclerotinia homoeocarpa with modified Ce6 was evaluated. The treatment was incorporated into potato dextrose agar (PDA) to the desired concentration. Then, plugs of S. homoeocarpa isolates (3 isolates were tested in total) with a diameter of 5 mm were inoculated into the center of the modified petri dishes and incubated at 21 °C in the dark for 24 h. After 24 h, one set of petri dishes (in triplicate) was placed in the dark and one set was placed under light for the remaining experiment (all experiments were conducted at 21 °C). The radial growth of the fungus was monitored daily until the growth of S. homoeocarpa on the unmodified PDA reached the edge of the petri dish. Illumination was provided by fluorescent lamps emitting approximately 180 μmol / m2 / s of photosynthetically active radiation (PAR).

[0752] Liquid medium protocol: The control of Sclerotinia homoeocarpa with modified chlorin was evaluated. Treatments at the desired concentrations were prepared in phosphate-buffered saline (PBS) in 24-well plates (in duplicate for dark and light incubations). Then, plugs of S. homoeocarpa isolates (3 isolates were tested in total) with a diameter of 5 mm were inoculated into the PBS and incubated at 21 °C in the dark for 2 h. After 2 h, one of the 24-well plates (with isolates in triplicate) was placed in the dark and one 24-well plate was placed under light for 1 h (all experiments were conducted at 21 °C). After illumination, 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 lamps emitting approximately 1000 μmol / m2 / s of photosynthetically active radiation (PAR).

[0753] Table 13A. Effects of modified Ce6 derivatives on Sclerotinia homoeocarpa

[0754]

[0755] Table 13B. Effects of modified Ce6 derivatives on Sclerotinia homoeocarpa

[0756]

[0757] The modified Ce6 compounds in Tables 13A and 13B can be used in the film-forming combinations and compositions of this specification.

[0758] Example 14:

[0759] Antibacterial Activity of Modified Ce6 Photosensitizer

[0760] Experiments were conducted to evaluate the control of the Gram-negative bacterial plant pathogen Pseudomonas syringae pv. tabaci by modified Ce6. Treatments at the desired concentrations were prepared in phosphate-buffered saline (PBS) in 96-well plates. The bacterial suspension was inoculated into the PBS and incubated at 28 °C in the dark for 30 minutes. After 30 minutes, the 96-well plates were placed under light (at 21 °C) for 1 hour. Separate plates prepared simultaneously were kept in the dark without light and used as dark controls. After light exposure, the bacterial suspension was serially diluted, and 10 μL of each dilution was evenly spread on tryptic soy agar (TSA) plates and placed in an incubator at 28 °C in the dark 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 an LED lamp (Heliospectra RX30) emitting approximately 1000 μmol / m 2 / s photosynthetically active radiation (PAR).

[0761] The modified Ce6 evaluated was Ce6-mixed-DMAE 15,17 amide, Ce6-bis-DMAE 15,17 amide and Ce6-mono-DMAE 15 amide. The results are shown in Table 14.

[0762] Table 14. Effects of Modified Ce6 Derivatives on Dollar Spot

[0763]

[0764] It can be seen that all forms of Ce6 DMAE amides (i.e., Ce6-mixed-DMAE 15,17 amide, Ce6-bis-DMAE 15,17 amide or Ce6-mono-DMAE 15 amide) can be used and the relative inactivation obtained is the same. This is because the data are presented as relative inactivation (i.e., the log ratio between the PBS control and the treatment). Since for all forms of Ce6 DMAE amides, the treatment killed all the bacteria leaving no colony-forming units, the value was set to 1 CFU / mL so as not to generate mathematical errors. Thus, the degree of inactivation depends on the control count and hence the values are the same between treatments. However, these experiments show that all forms of Ce6 DMAE amides are active against Gram-negative bacteria.

[0765] The modified Ce6 compound of Table 14 can be used in the film-forming combinations and compositions of this specification.

[0766] Example 15

[0767] Effect of the treated materials on the salt stress tolerance of strawberry plants (Fragaria x ananassa)

[0768] In this example, the effect of the modified chlorophyllide compound on strawberry plants (Fragaria x ananassa) cv Delizz was tested. The experiment was carried out in a greenhouse. The test was designed to determine the activity of the compound on the salt stress tolerance of strawberry plants.

[0769] In the experiment, the seedlings of strawberry plants were grown in 5-inch plastic pots filled with a professional soil mixture (LC 1 Sunshine, Sungro Horticulture, Canada) and regularly irrigated with fertilized water. The strawberry plants at the 4- to 5-leaf stage were treated with foliar application of three different formulations using a handheld spray bottle and provided with uniform coverage. The plants were sprayed once every 7 days. 24 hours after the first spray, the plants were exposed to salinity stress by soaking the plant roots in a 15 mM sodium chloride solution. The salinity level was gradually increased to 20 mM NaCl and the salt soaking was carried out at intervals of 5 to 7 days. The plants were harvested 3 weeks after the last foliar spray. A surfactant was added to each treated material. The experiment was carried out in a completely randomized design and each treated material was replicated 5 times.

[0770] Table 15: Effect of the treated materials on the salt stress tolerance of strawberry plants (Fragaria x ananassa).

[0771] # Treated material Aboveground fresh biomass, increased % 1 Salt control 0 2 <![CDATA[0.05% Cu - Ce6 - mixed - DMAE 15,17 amide + 0.05% surfactant]]> 12 3 <![CDATA[0.05% Ce6 - mono - 3TP - PEG 400 15 amide + 0.05% surfactant]]> 22 4 <![CDATA[0.05% Cu-Ce6-monor-3TP-PEG 400 15 amide + 0.05% surfactant]]> 11

[0772] The strawberry plants treated with the tested chlorophyllide compound showed enhanced tolerance to salt stress.

[0773] The modified Ce6 compound of Table 15 can be used in the film-forming combinations and compositions of this specification.

[0774] Example 16

[0775] Effect of the treated materials on the drought stress tolerance of strawberry (Fragaria x ananassa)

[0776] In this example, the effect of the modified chlorophyllide compound on strawberry plants (Fragaria x ananassa) cv Delizz was tested. The experiment was carried out in a greenhouse. The test was designed to determine the activity of the compound on the drought stress tolerance of strawberry plants.

[0777] In the experiment, strawberry plant seedlings were grown in 5-inch plastic pots filled with a professional soil mix (Sunshine Mix LC1 by Sun Gro Horticulture Canada) and regularly irrigated with fertilized water. Strawberry plants at the 4- to 5-leaf stage were treated with 3 foliar applications of different Suncor formulations using a handheld spray bottle and provided with uniform coverage. The plants were sprayed every 7 days. After the first leaf treatment and during the duration of the experiment, the strawberry plants were exposed to reduced moisture conditions (drought stress) until the wilting point (20 to 30% soil moisture capacity - SMC) and then watered to 50% SMC. The plants were harvested 3 weeks after the last foliar spray. A surfactant was added to each treatment. The experiment was conducted in a completely randomized design with seven replicates for each treatment.

[0778] Table 16: Effect of treatments on the tolerance of strawberry plants to drought stress

[0779] # Treated material Aboveground fresh biomass, % increase 1 Drought control 0 2 <![CDATA[0.05% Ce6 - mixed - DMAE 15,17 amide + 0.05% surfactant]]> 12 3 <![CDATA[0.05% Cu-Ce6-Mixed-DMAE 15,17 Amide + 0.05% Surfactant]]> 26 4 <![CDATA[0.05% Ce6 - mono - 3TP - PEG 400 15 amide + 0.05% surfactant]]> 12 5 <![CDATA[0.05% Cu-Ce6-Mono-3TP-PEG 400 15 amide + 0.05% surfactant]]> 14 6 0.05% surfactant 4

[0780] Strawberry plants treated with the tested chlorophyllin compounds showed enhanced tolerance of the plants to drought stress.

[0781] The modified Ce6 compounds of Table 16 can be used in the film-forming combinations and compositions of this specification.

[0782] Example 17

[0783] Effect of treatments on the tolerance of tomato plants (Solanum lycopersicum) cv. Tiny Tim to heat stress

[0784] The experiment was conducted in a growth chamber under controlled conditions. The trial was designed to determine the activity of the compounds on the tolerance of tomato plants to heat stress.

[0785] In the experiment, tomato plants cv. Tiny Tim were grown in a greenhouse at a temperature of 24 to 26 °C. The tomato seedlings were transplanted into 5” plastic pots containing an industrial soil mixture (Sunshine LC 1, Sun Gro Horticulture, Canada). At the 5- to 6-leaf stage, the plants were treated with the test solution using a handheld spray bottle (sprayed until runoff on the leaves) to provide uniform coverage. Forty-eight hours after spraying, the plants were moved into a growth chamber and exposed to heat stress for 10 days. The tomato plants were watered regularly to avoid water shortage. Ten days later, the tomato plants were transferred back to the greenhouse and treated a second time with the test solution. Forty-eight hours after the second spraying, the plants were placed in the growth chamber and exposed to heat stress for another 10 days. Growth chamber conditions: 16-hour / 8-hour light / dark photoperiod; temperature during darkness 19 °C; temperature during light - gradually increased from 19 °C to 37 °C within 4 hours, 37 °C for 8 hours, and then gradually decreased to 19 °C. The foliar treatment (spraying) was applied 2 times. A surfactant was added to each treatment. The experiment was conducted in a completely randomized design with six replicates for each treatment.

[0786] Table 17: Effect of chlorophyllin preparations on the tolerance of tomato plants to heat stress.

[0787] # Treated material Aboveground fresh biomass, % increase 1 Heat control 0 2 <![CDATA[0.05% Cu - Ce6 - mixed - DMAE 15,17 amide + 0.05% surfactant]]> 11 3 <![CDATA[0.05% Ce6 - mono - 3TP - PEG 400 15 amide + 0.05% surfactant]]> 10 4 <![CDATA[0.05% Cu-Ce6-monol-3TP-PEG 400 15 amide + 0.05% surfactant]]> 10 5 0.05% surfactant 3

[0788] Compared with the untreated control, the new chlorophyllin preparation enhanced the tolerance of tomato plants to heat stress and increased plant biomass.

[0789] The modified Ce6 compounds in Table 17 can be used in the film-forming combinations and compositions of this specification.

[0790] Example 18

[0791] Effect of treatments on the tolerance of Kentucky bluegrass (Poa pratensis) to salt stress

[0792] Kentucky bluegrass (Poa pratensis) was grown under greenhouse conditions for approximately 3 weeks. After 3 weeks, the plants were sprayed with the preparation and left for 24 hours, then the pots were placed in a 170 mM NaCl solution until the soil was saturated. The salt application was repeated after 7 days, for a total of 2 salt applications. The salinity stress was evaluated based on a turf quality rating from 1 to 9; where 1 = dead brown turf; 6 = minimally acceptable turf quality (based on the standards of a golf course or sports field); 9 = thick dark green turf (healthy). The data are the average of 5 replicates.

[0793] Table 18: Effect of salt stress on turf quality

[0794] Treated material Turf quality <![CDATA[0.1%Ce6Na3]]> 6 <![CDATA[0.1% Zn-Ce6-Mixed-DMAE 15,17 Amide]]> 5.8 <![CDATA[0.1% Cu - Ce6 - mixed - DMAE 15,17 amide]]> 6 <![CDATA[0.1% Cu-Ce6-monol-3TP-PEG 400 15 amide]]> 6.2 Untreated control 5

[0795] The modified Ce6 compound of Table 18 can be used in the film-forming combinations and compositions of this specification.

[0796] Example 19

[0797] Effect of treated substances on silkworms

[0798] Experiments were conducted to evaluate the toxicity of photosensitizer compounds to the larvae of the silkworm (Bombyx mori (L.)).

[0799] A colony of third-instar larvae of the silkworm (Bombyx mori) was purchased from the distributor Recorp Inc. (Ontario, Canada) and fed on fresh mulberry leaves (Morus rubra) for 2 days before treatment.

[0800] Mulberry twigs were collected from outdoor-grown trees without any pesticide treatment. The fresh mulberry twigs were washed in tap water and then air-dried.

[0801] Small mulberry twigs (8 to 10 leaves) were cut from mature healthy young branches and inserted into 50 ml plastic bottles 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 test solution until runoff, and the vials with the sprayed twigs were placed in a 1 L transparent plastic container lined with filter paper.

[0802] Homogenized silkworm larvae (3rd instar) were sprayed separately and released into the container on the treated mulberry twigs. The insects were treated with a soft fine paintbrush. The containers containing the plant twigs and insects were covered with white mesh lead.

[0803] All treated substances were applied in the form of a fine spray using a 2 oz handheld spray bottle (ULINE Canada Inc.). The water-treated substance was used as a control.

[0804] The containers containing the twigs and insects were randomly placed on a metal rack equipped with LED lights and immediately irradiated with light at 450 μmol m -2 s -1 The experiment was conducted in a plant growth chamber at a temperature of 24 to 26 °C and a photoperiod of 12 hours of LED light and 12 hours of darkness. The silkworms were allowed to feed on the treated mulberry leaves for 48 hours. The food source was changed once a day. A completely randomized design was used in the experiment, where each treated substance was repeated four times with 10 insects per replicate. The larvae were considered dead if no movement was detected after mechanical stimulation with a paintbrush. The number of live and dead insects was recorded. The insect mortality was evaluated up to 72 hours after treatment (hours after treatment, HAT). The phytotoxicity symptoms of the mulberry leaves were evaluated.

[0805] Zn-Ce6-mixed-DMAE was formulated with propylene glycol and Pluronic F-127 surfactant 15,17Amide and Pd-Ce6-Mixed-DMAE 15,17 Amide to improve solubility in water.

[0806] Table 19: Effects of photosensitizers on the mortality rate of silkworm larvae.

[0807]

[0808] *Surfactant (0.5% propylene glycol + 0.1% Pluronics F-127)

[0809] Treatment 0.1% Ce6-Mixed-DMAE 15,17 Amide and 0.1% Pd-Ce6-Mixed-DMAE 15,17 The larval mortality rates caused by amide + 0.5% propylene glycol + 0.1% Pluronic F127 were 57.5% and 35% respectively, and the larval weight was significantly reduced.

[0810] The treated mulberry branches did not show any visible phytotoxic symptoms. None of the test preparations were phytotoxic to the plant leaves.

[0811] The modified Ce6 compounds in Table 19 can be used in the film-forming combinations and compositions of this specification.

[0812] Example 20

[0813] Control of the fungal pathogen Cgm of Nicotiana benthamiana

[0814] The control of the fungal phytopathogen Colletotrichum gloeosporioides ATC 20767 (Cgm) on the host plant Nicotiana benthamiana after treatment with modified chlorin e6 compounds was evaluated. Approximately 2 hours before inoculation with a spore suspension of Cgm, the Nicotiana benthamiana plants were treated. The plants were then exposed to light for 24 hours, followed by dark incubation until obvious disease symptoms appeared on the water-treated control plants. Once the disease symptoms were obvious, the lesions were counted and the leaf area was measured to determine the number of lesions per square centimeter of leaf area. Four replicate plants were used for each treatment, and the plants were randomized under the light source. Illumination was provided by LED lights emitting approximately 180 μmol / m 2 / s photosynthetically active radiation (PAR). The results are shown in Tables 20A, 20B, and 20C.

[0815] Table 20A: Effects of modified Ce6 compounds on Colletotrichum orbiculare.

[0816] Treated material Disease inhibition rate, % <![CDATA[0.05% Ce6 - mixed - DMAE 15,17 amide]]> 87 <![CDATA[0.05% Zn-Ce6-Mixed-DMAE 15,17 Amide]]> 35 <![CDATA[0.05% Pd-Ce6 - Hybrid - DMAE 15,17 Amide]]> 1 <![CDATA[0.05% Cu - Ce6 - mixed - DMAE 15,17 amide]]> 69 Untreated control 0

[0817] Surfactants can be added to the solution to increase the solubility of the compound and its spreading on the leaf surface.

[0818] Table 20B: Effect of modified Ce6 compounds on Colletotrichum orbiculare.

[0819] Treated material Disease inhibition rate, % Untreated control 0 <![CDATA[0.05% Ce6 - mixed - DMAE 15,17 amide + surfactant]]> 72 <![CDATA[0.05% Zn-Ce6-Mixed-DMAE 15,17 Amide + Surfactant]]> 97 <![CDATA[0.05% Pd-Ce6-Mixed-DMAE 15,17 Amide + Surfactant]]> 87 <![CDATA[0.05% Cu - Ce6 - Mixed - DMAE 15,17 Amide + Surfactant]]> 96 <![CDATA[0.05% Ce6 - mono - DMAE 15 amide + surfactant]]> 94 Surfactant -29

[0820] * Surfactant (0.5% propylene glycol + 0.1% Pluronics F-127)

[0821] In another experiment, PEG-modified Ce6 compounds were tested against Cgm.

[0822] Table 20C: Effect of modified Ce6 compounds on Colletotrichum orbiculare

[0823] Treated material Disease inhibition rate, % Control 0 <![CDATA[0.05% Ce6 - mono - 3TP - PEG 400 15 amide + surfactant]]> 63 <![CDATA[0.05% Zn-Ce6-monor-3TP-PEG 400 15 amide + surfactant]]> 26 Surfactant 12

[0824] * Surfactant (0.5% propylene glycol + 0.1% Pluronics F-127)

[0825] The modified Ce6 compounds of Tables 20A, 20B, and 20C can be used in the film-forming combinations and compositions of this specification.

[0826] Example 21

[0827] Control of the bacterial pathogen Pst of Arabidopsis thaliana

[0828] Arabidopsis plants were grown under a 12 h:12 h, light:dark photoperiod, under LED lights (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), allowed to dry for 2 h, and then sprayed with Pseudomonas syringae pv. tabaci (OD 0.08 diluted in 10 mM MgCl2). The plants were kept under a plastic dome until symptoms appeared. The severity of the disease was evaluated by counting the number of yellow leaves / plant. The data are the average of 3 replicates.

[0829] Table 21: Effect of modified Ce6 compounds on the bacterial pathogen Pst of Arabidopsis thaliana

[0830] Treated material Disease inhibition rate, % Untreated control 0 <![CDATA[0.05% Ce6 - mixed - DMAE 15,17 amide + surfactant]]> 48 <![CDATA[0.05% Zn-Ce6-Mixed-DMAE 15,17 Amide + Surfactant]]> 45 <![CDATA[0.05% Pd-Ce6 - mixed - DMAE 15,17 amide + surfactant]]> 52 <![CDATA[0.05% Cu - Ce6 - mixed - DMAE 15,17 amide + surfactant]]> 34 <![CDATA[0.05% Ce6 - mono - DMAE 15 amide + surfactant]]> 56 <![CDATA[0.05% Ce6 - mono - 3TP - PEG 400 15 amide + surfactant]]> 22 <![CDATA[0.05% Zn-Ce6-Mono-3TP-PEG 400 15 Amide + Surfactant]]> 34 Surfactant 0

[0831] * Surfactant (0.5% propylene glycol + 0.1% Pluronics F-127)

[0832] The modified Ce6 compounds of Table 21 can be used in the film-forming combinations and compositions of this specification.

[0833] Example 22

[0834] Control of Pseudomonas syringae pv. tabaci (Pst) in Nicotiana benthamiana

[0835] The control of Pseudomonas syringae pv. tabaci (Pst) in the host plant Nicotiana benthamiana after treatment with the modified chlorin e6 compound was evaluated. Approximately 2 hours before inoculation with a spore suspension of Cgm, the Nicotiana benthamiana plants were treated. The plants were then exposed to light for 24 hours, followed by incubation in the dark until distinct disease symptoms appeared on the water-treated control plants. Once the disease symptoms were distinct, the lesions were counted and the leaf area was measured to determine the number of lesions per square centimeter of leaf area. Four replicate plants were used for each treatment, and the plants were randomized under the light source. Illumination was provided by LED lights emitting approximately 180 μmol / m 2 / s photosynthetically active radiation (PAR). The results are shown in Table 22.

[0836] Table 22: Effects of modified Ce6 on Pseudomonas syringae pv. tabaci in Nicotiana benthamiana

[0837] Disease inhibition rate, % Untreated control 0 <![CDATA[0.1% Zn-Ce6-monor-3TP-PEG 400 15 amide]]> 47 <![CDATA[0.1% Ce6 - mono - 3TP - PEG 400 15 amide]]> 63 <![CDATA[0.1% Pd-Ce6 - mixed - DMAE 15,17 amide + surfactant]]> 65 Surfactant 34

[0838] *Surfactant (0.5% propylene glycol + 0.1% Pluronics F-127)

[0839] The modified Ce6 compounds of Table 22 can be used in the film-forming combinations and compositions of this specification.

[0840] Example 23

[0841] Control of Rose aphids with the modified Ce6 compound

[0842] Experiments were conducted to evaluate the toxicity of the chlorine derivative against the insect pest Rose aphids (Marcosiphum rosae). The experiments were carried out on Rosa cv Knockout, Double red plants infested with aphids. The experiments were conducted in a plant nursery (Crop Inspection Service, California, Valley center, USA). The experimental plants were not exposed to insecticide treatment before testing.

[0843] The experimental Rosa plants were grown outdoors in 3-gallon black plastic pots filled with Sunshine #4 soil mix. The plants were irrigated daily and fertilized twice a week with 200 ppm of soluble fertilizer 20-20-20.

[0844] In the experiment, newly infested aphid nymphs on the shoot tips of Rosa plants were used. The number of Macrosiphum rosae in the colonies aggregated on the shoot tips was counted before treatment, and the treated shoots were covered with white 4x6” mesh tulle bags (ULINE, USA) to avoid infestation by natural enemies. The bags were kept on the shoots during the trial period. At the start of the experiment, the aphid populations (on the shoots) were considered uniform, with each shoot having 25 to 28 aphids. A completely randomized design was used for 6 replicate plants (one shoot per plant).

[0845] The treatments were applied using a 2-ounce plastic hand-held spray bottle (Natural Cylinder Spray Bottle, ULINE, Canada) to deliver a uniform fine spray on the plant shoots. The Rosa shoots were thoroughly sprayed with the test treatments and exposed to direct sunlight. The second application of the treatment was carried out using the same method 7 days after the first application.

[0846] The effect of the treatments on the insects was determined by counting the live insects 7 days after the first treatment and 14 days after the second treatment.

[0847] The phytotoxicity of the plants was evaluated 6 days after each foliar spray.

[0848] Table 23. Effect of chlorophyll derivatives on Macrosiphum rosae.

[0849]

[0850] Compared with the water control treatment, treatment with 0.1% Ce6-mono-3TP-PEG400 15 amide and 0.1% Ce6-mixed-DMAE 15 ,17 amide showed good efficacy against Macrosiphum rosae and inhibited the insect population.

[0851] The treated Rosa shoots did not show any visible phytotoxicity symptoms.

[0852] The modified Ce6 compounds in Table 23 can be used in the film-forming combinations and compositions of this specification.

[0853] Example 24

[0854] Control of cucumber mosaic virus on Capsicum annuum plants

[0855] At the 3-4 leaf stage, transplant the seedlings of dwarf bell pepper "Golden baby belle hybrid" into pots filled with a premix and place them in a growth chamber at a temperature of 26 / 23 °C (day / night), a relative humidity of 70%, a light intensity of 270 μmol m -2 s -1 , and a photoperiod of 12 hours. On the 7th, 14th, 21st, and 28th days after transplantation, a formulation containing 0.1 wt% Ce6-mixed-DMAE 15,17 amide and a surfactant was applied foliarly using a handheld sprayer until the leaf surface was completely covered with the solution (~2.5 mL / pot). The plants were watered thoroughly by hand irrigation and fertilized every 2 weeks with 0.73 g of nitrogen m -2 from 28-8-18 complete fertilizer. Cucumber mosaic virus (CMV) inoculation was carried out 2 hours after the third application. For inoculation, the leaves (~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 silicon carbide was added to the mixture. It was applied to the upper surface of the top 3 newly developed leaves of the pepper using a cotton swab. A randomized block design with 4 replicates was used. The pots were randomly rearranged in the growth chamber twice a week. The severity of CMV disease development in the leaves was measured on the 19th, 21st, 28th, 35th days, and at the end of the experiment. 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.

[0856] Table 24: Severity of cucumber mosaic virus (CMV) disease

[0857]

[0858] *Surfactant: 0.1% APG325N

[0859] The modified Ce6 compounds of Table 24 can be used in the film-forming combinations and compositions of this specification.

[0860] Example 25

[0861] Effect of PP IX and modified PP IX on Pseudomonas syringae pv. tabaci

[0862] In this example, the control of the Gram-negative bacterial plant pathogen Pseudomonas syringae pv. tabaci with PP IX and modified PP IX was evaluated in the presence and absence of a chelating agent. Treatments at the desired concentrations were prepared in phosphate buffered saline (PBS) in 96-well plates. The bacterial suspension was inoculated into the PBS and incubated for 30 minutes at 28 °C in the dark. After 30 minutes, the 96-well plates were placed under light (at 21 °C) for 1 hour. After illumination, the bacterial suspension was serially diluted and 10 μL of each dilution was evenly spread on tryptic soy agar (TSA) plates and placed in an incubator at 28 °C in the dark 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 an LED lamp (Heliospectra RX30) emitting approximately 1000 μmol / m 2 / s photosynthetically active radiation (PAR). The results are summarized in Table 25.

[0863] Table 25: Effects of 10 μM PP IX and PP IX derivatives on Pseudomonas syringae

[0864] Compound Log CFU / ml PBS (control) 8.7 10 μM PpIX disodium salt 7.4 10 μM (PpIX-mono-DMAE:PpIX-bis-DMAE - 50:50) 8.7 10 μM (PpIX-mono-DMAE:PpIX-bis-DMAE - 20:80) 5.5 10 μM PpIX disodium salt + 5 mM NaEDTA 3.8 10 μM (PpIX-mono-DMAE:PpIX-bis-DMAE - 50:50) + 5 mM NaEDTA 3.1 10 μM (PpIX-mono-DMAE:PpIX-bis-DMAE - 20:80) + 5 mM NaEDTA 0.0

[0865] * The "PP IX - mono" type compounds are a mixture (approx. 50:50) of mono-substituted PP IX at the C 15 position and mono-substituted PP IX at the C 17 position.

[0866] The PP IX and modified PP IX compounds of Table 25 can be used in the film-forming combinations and compositions of this specification.

[0867] Example 26

[0868] Effects of PP IX and modified PP IX on dollar spot

[0869] In this example, the control of dollar spot pathogen (Sclerotiniahomoeocarpa) with PP IX and modified PP IX was evaluated. Treatments at the desired concentrations were prepared in phosphate buffered saline (PBS) in 24-well plates (in duplicate for dark and light incubations). Then, plugs of 5 mm diameter of dollar spot isolates (3 isolates were tested in total) 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 triplicate isolates) was placed in the dark and one 24-well plate was placed under light for 1 hour (all experiments were conducted at 21 °C). After illumination, the fungal plugs were removed from 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 the dollar spot pathogen reached the edge of the petri dish. Illumination was provided by LED lights emitting approximately 1000 μmol / m2 / s of photosynthetically active radiation (PAR). The results are summarized in Tables 26A and 26B.

[0870] Table 26A: Results in the dark (no exposure)

[0871]

[0872] Notes to the above table:

[0873] 1 Treatments were prepared in phosphate buffered saline (PBS), incubated for 2 hours on an oscillator (200 rpm) in the dark and then kept for 1 hour without shaking in the dark.

[0874] 2 The mean values were calculated based on 3 fungal isolates repeated 3 times with 2 measurements per repeat (18 measurements in total)

[0875] 3 The mean values represent the growth that occurred between 24 and 48 hours of incubation at 21 °C

[0876] 4 Inhibition rate % calculated relative to the unmodified control

[0877] * The "PP IX - single" type compound is a mixture (approx. 50:50) of mono-substituted PP IX at the C 15 position and mono-substituted PP IX at the C 17 position.

[0878] Table 26B: Results under light (exposed to light for 1 hour)

[0879]

[0880] Notes to the above table:

[0881] 1 Prepare the treatment in phosphate buffered saline (PBS), incubate for 2 hours on a shaker (200 rpm) in the dark, and then expose to light (Helios, 1000 PAR) for 1 hour.

[0882] 2 Calculate the mean based on 3 fungal isolates repeated 3 times, with 2 measurements per repetition (18 measurements in total)

[0883] 3 The mean represents the growth that occurs between 24 and 48 hours of incubation at 21 °C.

[0884] 4 Inhibition rate % calculated relative to the unmodified control

[0885] * The "PP IX - mono" type compound is a mixture (approx. 50:50) of PP IX monosubstituted at the C 15 position and PP IX monosubstituted at the C 17 position.

[0886] The PP IX and modified PP IX compounds of Tables 26A and 26B can be used in the film - forming combinations and compositions of this specification.

[0887] Example 27

[0888] Effect of PP IX and modified PP IX on Colletotrichum gloeosporioides

[0889] The control of the fungal plant pathogen Colletotrichum gloeosporioides ATC 20767 (Cgm) on the host plant Nicotiana benthamiana after treatment with modified PP IX compounds was evaluated. Approximately 2 hours before inoculation with a spore suspension of Cgm, the Nicotiana benthamiana plants were treated. Then the plants were exposed to light for 24 hours, followed by incubation in the dark until obvious disease symptoms appeared on the water - treated control plants. Once the disease symptoms were obvious, the lesions were counted and the leaf area was measured to determine the number of lesions per square centimeter of leaf area. Four replicate plants were used for each treatment, and the plants were randomized under the light source. Illumination was provided by LED lights emitting approximately 180 μmol / m 2 / s photosynthetically active radiation (PAR). The results are shown in Table 27.

[0890] Table 27: Effect of modified PP IX compounds on Colletotrichum gloeosporioides.

[0891] Treated material % Inhibition Untreated control 0 0.05% (PpIX-mono-DMAE:PpIX-bis-DMAE - 20:80) 93 0.05% (PpIX-mono-DMAE:PpIX-bis-DMAE - 50:50) 89 <![CDATA[0.05% PP IX - mono - PEG 600 > 56 0.05% PpIX-mono-L-valine 50 0.05% PpIX-mono-glycine 35

[0892] * The "PP IX - mono" type compound is a mixture of PP IX monosubstituted at the C 15 position and PP IX monosubstituted at the C 17A mixture of mono-substituted PP IX at the position (about 50:50).

[0893] The PP IX and modified PP IX compounds of Table 27 can be used in the film-forming combinations and compositions of this specification.

[0894] Abbreviations of modified Ce6 and PP IX compounds:

[0895]

[0896]

[0897]

[0898]

[0899]

[0900]

[0901]

[0902] *All Ce6 compounds have the (S),(S) stereochemistry of two asymmetric carbons

[0903] All publications, patents, and patent documents cited above are incorporated herein by reference 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, those skilled 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, 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 oxygen-impermeable when in a non-hydrated state; an antioxidant; and a liquid carrier in which the photosensitizer, the film-forming agent, and the antioxidant are dissolved and / or dispersed, wherein the film-forming agent is selected from carboxymethyl cellulose, guar gum, polyvinyl alcohol (PVOH) having a degree of hydrolysis equal to or greater than 70%, and combinations thereof.

2. The composition according to claim 1, wherein the polyvinyl alcohol has an average molecular weight of 10 kDa to 200 kDa.

3. The composition according to claim 1, wherein the polyvinyl alcohol has an average molecular weight of 50 kDa to 100 kDa and a degree of hydrolysis equal to or greater than 99%.

4. The composition according to claim 1, wherein when in solution, the antioxidant is more reactive towards reactive oxygen species than the photosensitizer.

5. The composition according to claim 1, wherein when in a hydrated film, the antioxidant is more reactive towards reactive oxygen species than the photosensitizer.

6. The composition according to claim 1, wherein 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, tert-butyl-hydroxyquinone, butylated hydroxytoluene, butylated hydroxyanisole, α-tocopherol, D-α-tocopherol polyethylene glycol succinate, retinyl palmitate, β-carotene, isoascorbic acid, sodium isoascorbate, sodium ascorbate, ascorbic acid, glutathione, superoxide dismutase, catalase, sodium azide, 1,4-diazabicyclo[2.2.2]octane (DABCO), and combinations thereof.

7. The composition according to claim 1, wherein the antioxidant comprises a phenolic antioxidant.

8. The composition according to claim 7, wherein 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, lignosulfonates, and combinations thereof.

9. The composition according to any one of claims 1 to 8, wherein the photosensitizer is metallated with a selected metal such that, in response to light and oxygen exposure, the metallated photosensitizer generates reactive oxygen species.

10. The composition according to claim 9, wherein 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.

11. The composition according to claim 9, wherein 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).

12. The composition according to any one of claims 1 to 8, wherein the photosensitizer is metal-free and is selected such that in response to light and oxygen exposure, the metal-free photosensitizer generates reactive oxygen species.

13. The composition according to any one of claims 1 to 8, wherein the photosensitizer comprises a reduced porphyrin.

14. The composition according to claim 13, wherein the photosensitizer is selected from the group consisting of chlorophyllide, bacteriochlorophyll, isobacteriochlorophyll, corrin, corphin, and mixtures thereof.

15. The composition according to claim 14, wherein the photosensitizer is chlorophyllide.

16. The composition according to claim 15, wherein the chlorophyllide is chlorophyllide e6 or a modified chlorophyllide e6.

17. The composition according to any one of claims 1 to 8, wherein the photosensitizer comprises a porphyrin.

18. The composition according to claim 17, wherein the porphyrin is protoporphyrin or meso-tetra-(4-sulfonatophenyl)porphyrin (TPPS).

19. The composition according to claim 17, wherein the photosensitizer comprises protoporphyrin IX (PP IX) or a modified PPIX.

20. The composition according to any one of claims 1 to 8, wherein the liquid carrier is an aqueous carrier.

21. The composition according to claim 20, wherein the aqueous carrier comprises at least one water-soluble compound that increases the solubility and / or dispersibility of at least one of the photosensitizer, the film-forming agent, and the antioxidant in the aqueous carrier.

22. The composition according to claim 20, wherein the aqueous carrier comprises an oil and is an oil-in-water emulsion.

23. The composition according to claim 22, wherein the oil is selected from the group consisting of mineral oil, vegetable oil, and mixtures thereof.

24. The composition according to claim 23, wherein the vegetable 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.

25. The composition according to claim 23, wherein the mineral oil comprises a mineral oil selected from the group consisting of paraffin oil, branched paraffin oil, naphthenic oil, aromatic oil, and mixtures thereof.

26. The composition according to claim 23, wherein the oil comprises poly-α-olefin (PAO).

27. The composition according to any one of claims 1 to 8, which further comprises a chelating agent.

28. The composition according to claim 27, wherein 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'-dipentanedioic acid (EDDG) or an agriculturally acceptable salt thereof, ethylenediamine-N,N'-dimalonic 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.

29. The composition according to claim 28, wherein the chelating agent is metallized.

30. The composition according to claim 28, wherein the chelating agent is metal-free.

31. The composition according to any one of claims 1 to 8, further comprising a surfactant.

32. The composition according to claim 31, 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.

33. The composition according to claim 32, wherein the film-forming agent is present in an amount between 0.01 wt% and 20 wt% based on the total weight of the composition.

34. The composition according to claim 32, wherein the photosensitizer is present in an amount between 0.01 wt% and 10 wt% based on the total weight of the composition.

35. The composition according to claim 32, wherein the antioxidant is present in an amount between 0.01 wt% and 5 wt% based on the total weight of the composition.

36. The composition according to any one of claims 1 to 8, wherein the composition is a ready-to-use composition to be applied to the plant.

37. The composition according to any one of claims 1 to 8, wherein the composition is a concentrate to be diluted before being applied to the plant.

38. The composition according to any one of claims 1 to 8, wherein the plant is an adult plant.

39. The composition according to any one of claims 1 to 8, wherein the plant is a non-woody crop plant, a woody plant, or a turfgrass.

40. The composition according to any one of claims 1 to 8, wherein when in an environment with a relative humidity below about 50% RH, the film is substantially oxygen-impermeable.

41. The composition according to any one of claims 1 to 8, wherein when in an environment with a relative humidity below about 60% RH, the film is substantially oxygen-impermeable.

42. The composition according to any one of claims 1 to 8, wherein the film is substantially permeable to oxygen when in a hydrated state.

43. The composition according to claim 42, wherein the film is substantially permeable to oxygen when in an environment with a relative humidity between 50% RH and 100% RH.

44. The composition according to claim 43, wherein the film is substantially permeable to oxygen when in an environment with a relative humidity between 60% RH and 100% RH.

45. The composition according to any one of claims 1 to 8, which is for application to the plant by at least one of irrigation, spraying, misting, sprinkling, pouring, and dipping.

46. The composition according to any one of claims 1 to 8, which is applied to the non-renewable parts of the plant.

47. The composition according to any one of claims 1 to 8, wherein after the composition is applied to the plant, the liquid carrier is removed by air drying.

48. The composition according to any one of claims 1 to 8, wherein when at least a part of the liquid carrier is removed from the composition, the film-forming agent forms a film.

49. The composition according to any one of claims 1 to 8, which is for promoting the health of a plant.

50. The composition according to claim 49, wherein promoting the health of the plant includes preventing or inhibiting the growth of microbial pathogens of the plant.

51. The composition according to claim 50, wherein the microbial pathogens include fungal pathogens, bacterial pathogens, viruses, viroids, virus-like organisms, or phytoplasmas.

52. The composition according to claim 51, wherein the microbial pathogen is a fungal pathogen.

53. The composition according to claim 51, wherein the microbial pathogen is a bacterial pathogen.

54. The composition according to claim 49, wherein promoting the health of the plant includes increasing the plant's resistance to one or more abiotic stresses.

55. The composition according to claim 54, wherein the one or more abiotic stresses are selected from the group consisting of cold stress, heat stress, water stress, transplant shock stress, low light stress, photooxidative stress, drought stress, and salinity stress.

56. The composition according to any one of claims 1 to 8, wherein promoting the health of the plant includes controlling insect pests of the plant.

57. The composition according to claim 56, wherein the insect pests are selected from the group consisting of insects and insect larvae.

58. A method for promoting the health of a plant, which includes: applying to the plant a composition as defined in any one of claims 1 to 8; and removing at least a part of the aqueous carrier from the film-forming agent composition to form a film on the plant that is substantially impermeable to oxygen when in a non-hydrated state.

59. The method according to claim 58, wherein applying the composition to the plant is carried out by at least one of irrigation, spraying, misting, sprinkling, pouring, and dipping.

60. The method according to claim 58, wherein applying the composition to the plant comprises applying the composition to a non-renewable part of the plant.

61. The method according to claim 58, wherein removing at least a portion of the liquid carrier from the composition comprises exposing the plant to a low humidity environment, exposing the plant to heat, exposing the plant to air, an inert gas or a nitrogen stream, and allowing the composition to dry naturally on the plant.

62. The method according to claim 61, wherein removing at least a portion of the liquid carrier from the composition comprises allowing the composition to dry naturally on the plant.

63. The method according to claim 58, wherein promoting the health of the plant comprises preventing or inhibiting the growth of microbial pathogens of the plant.

64. The method according to claim 58, wherein promoting the health of the plant comprises inhibiting the growth of microbial pathogens of the plant.

65. The method according to claim 63, wherein the microbial pathogen comprises a fungal pathogen, a bacterial pathogen, a virus, a viroid, a virus-like organism or a phytoplasma.

66. The method according to claim 65, wherein the microbial pathogen is a fungal pathogen.

67. The method according to claim 65, wherein the microbial pathogen is a bacterial pathogen.

68. The method according to claim 58, wherein promoting the health of the plant comprises increasing the plant's resistance to one or more abiotic stresses.

69. The method according to claim 68, wherein the one or more abiotic stresses are selected from the group consisting of cold stress, heat stress, water stress, transplant shock stress, low light stress, photooxidative stress, drought stress and salinity stress.

70. The method according to claim 58, wherein promoting the health of the plant comprises controlling insect pests of the plant.

71. The method according to claim 70, wherein the insect pests are selected from the group consisting of insects and insect larvae.

72. Use of a composition for improving the health of a plant, the composition comprising: 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 oxygen-impermeable when in a non-hydrated state; an antioxidant; and a liquid carrier in which the photosensitizer, the film-forming agent and the antioxidant are dissolved and / or dispersed, wherein the film-forming agent is selected from carboxymethyl cellulose, guar gum, polyvinyl alcohol (PVOH) having a degree of hydrolysis equal to or greater than 70% and combinations thereof.

73. The use according to claim 72, wherein the polyvinyl alcohol has an average molecular weight of 10 kDa to 200 kDa.

74. The use according to claim 72, wherein the polyvinyl alcohol has an average molecular weight of 50 kDa to 100 kDa and a degree of hydrolysis equal to or greater than 99%.

75. Use according to any one of claims 72 to 74, wherein when in solution, the antioxidant is more reactive towards reactive oxygen species than the photosensitizer.

76. Use according to any one of claims 72 to 74, wherein when in a hydrated membrane, the antioxidant is more reactive towards reactive oxygen species than the photosensitizer.

77. Use according to any one of claims 72 to 74, wherein 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, tert-butyl-hydroxyquinone, butylated hydroxytoluene, butylated hydroxyanisole, α-tocopherol, D-α-tocopherol polyethylene glycol succinate, retinyl palmitate, β-carotene, isoascorbic acid, sodium isoascorbate, sodium ascorbate, ascorbic acid, glutathione, superoxide dismutase, catalase, sodium azide, 1,4-diazabicyclo[2.2.2]octane (DABCO), and combinations thereof.

78. Use according to any one of claims 72 to 74, wherein the antioxidant comprises a phenolic antioxidant.

79. Use according to claim 78, wherein 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, lignosulfonates, and combinations thereof.

80. Use according to any one of claims 72 to 74, wherein the photosensitizer is metallated with a selected metal such that, in response to light and oxygen exposure, the metallated photosensitizer generates reactive oxygen species.

81. Use according to claim 80, wherein 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.

82. Use according to claim 80, wherein 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).

83. Use according to any one of claims 72 to 74, wherein the photosensitizer is metal-free and is selected such that, in response to light and oxygen exposure, the metal-free photosensitizer generates reactive oxygen species.

84. Use according to any one of claims 72 to 74, wherein the photosensitizer comprises a reduced porphyrin.

85. The use according to claim 84, wherein the photosensitizer is selected from the group consisting of chlorophyllin, bacteriochlorophyll, isobacteriochlorophyll, corrin, corphin, and mixtures thereof.

86. The use according to claim 85, wherein the photosensitizer is chlorophyllin.

87. The use according to claim 86, wherein the chlorophyllin is chlorophyllin e6 or modified chlorophyllin e6.

88. The use according to any one of claims 72 to 74, wherein the photosensitizer comprises porphyrin.

89. The use according to claim 88, wherein the porphyrin is protoporphyrin or meso-tetra-(4-sulfonatophenyl) porphyrin (TPPS).

90. The use according to claim 88, wherein the photosensitizer comprises protoporphyrin IX (PP IX) or modified PPIX.

91. The use according to any one of claims 72 to 74, wherein the liquid carrier is an aqueous carrier.

92. The use according to claim 91, wherein the aqueous carrier comprises at least one water-soluble compound that increases the solubility and / or dispersibility of at least one of the photosensitizer, the film-forming agent, and the antioxidant in the aqueous carrier.

93. The use according to claim 91, wherein the aqueous carrier comprises oil and is an oil-in-water emulsion.

94. The use according to claim 93, wherein the oil is selected from the group consisting of mineral oil, vegetable oil, and mixtures thereof.

95. The use according to claim 94, wherein the vegetable 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.

96. The use according to claim 94, wherein the mineral oil comprises a mineral oil selected from the group consisting of paraffin oil, branched paraffin oil, naphthenic oil, aromatic oil, and mixtures thereof.

97. The use according to claim 94, wherein the oil comprises poly-α-olefin (PAO).

98. The use according to any one of claims 72 to 74, wherein the composition further comprises a chelating agent.

99. The use according to claim 98, wherein 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'-dipentanedioic acid (EDDG) or an agriculturally acceptable salt thereof, ethylenediamine-N,N'-dimalonic 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.

100. The use according to claim 99, wherein the chelating agent is metallized.

101. The use according to claim 99, wherein the chelating agent is metal-free.

102. The use according to any one of claims 72 to 74, wherein the composition further comprises a surfactant.

103. The use according to claim 102, 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.

104. The use according to any one of claims 72 to 74, wherein the film-forming agent is present in an amount between 0.01% by weight and 20% by weight, based on the total weight of the composition.

105. The use according to any one of claims 72 to 74, wherein the photosensitizer is present in an amount between 0.01% by weight and 10% by weight, based on the total weight of the composition.

106. The use according to any one of claims 72 to 74, wherein the antioxidant is present in an amount between 0.01% by weight and 5% by weight, based on the total weight of the composition.

107. The use according to any one of claims 72 to 74, wherein the composition is a ready-to-use composition to be applied to the plant.

108. The use according to any one of claims 72 to 74, wherein the composition is a concentrate to be diluted before being applied to the plant.

109. The use according to any one of claims 72 to 74, which is for application to the plant by at least one of irrigation, spraying, misting, sprinkling, pouring, and dipping.

110. The use according to any one of claims 72 to 74, wherein the plant is an adult plant.

111. The use according to any one of claims 72 to 74, wherein the composition is for application to the non-renewable parts of the plant.

112. Use according to any one of claims 72 to 74, wherein the plant is a non-woody crop plant, a woody plant or a turfgrass.

113. Use according to any one of claims 72 to 74, wherein after applying the composition to the plant, the liquid carrier is removed by air drying.

114. Use according to any one of claims 72 to 74, wherein when at least a portion of the liquid carrier is removed from the composition, the film-forming agent forms a film.

115. A method for promoting the health of a plant, comprising applying to the plant a composition as defined in any one of claims 1 to 8; and removing at least a portion of the liquid carrier from the film-forming composition of the film-forming agent to form a substantially oxygen-impermeable film.

Images