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WO2023012332A1 - Compositions pour le soin de plantes et leurs utilisations - Google Patents

Compositions pour le soin de plantes et leurs utilisations Download PDF

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Publication number
WO2023012332A1
WO2023012332A1 PCT/EP2022/072081 EP2022072081W WO2023012332A1 WO 2023012332 A1 WO2023012332 A1 WO 2023012332A1 EP 2022072081 W EP2022072081 W EP 2022072081W WO 2023012332 A1 WO2023012332 A1 WO 2023012332A1
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Prior art keywords
plant
care formulation
linked chitosan
chitosan
cross
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Inventor
Vladislav FOMENKO
Yuriy KARGAPOLOV
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Novochizol Sa
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Novochizol Sa
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom

Definitions

  • the invention relates to formulations for plant care, including plant care products (PCP) and substances useful in agriculture and plant growth and methods of preparation thereof.
  • PCP plant care products
  • Plant growth and development is adversely affected by different stressors that are either biotic (pests, diseases, weeds) or abiotic (lack or excess of moisture, low or high temperatures, salinity, heavy metals, other toxic substances, etc.).
  • the resulting loss in crop yield may be substantial.
  • chemical agents play the most important role. They act as highly effective pesticides, fertilizers or growth regulators. However, because they accumulate in soil, water and inside living organisms, their widespread use in agriculture has an adverse effect on the environment.
  • Chitin and its derivative chitosan are promising alternatives to chemical agents (Malerba and C er ana, 2020, Polysaccharides, 1, 21 30; https://doi.org/10.3390/polysaccharidesl010003).
  • Chitin is a long-chain, high molecular weight polysaccharide composed of N-acetyl-D-glucosamine and D-glucosamine. It is the main component of the exoskeleton of arthropods and of the cell wall of mushrooms.
  • Chitosan is derived from chitin by deacetylation.
  • chitosan-based treatments Different factors impact the effectiveness of chitosan-based treatments: molecular weight, chemical modifications, pH, concentration, chelating potential, and the type of microorganism that is targeted.
  • the use of chitosan in various crops is actively studied. Chitosan formulations have been developed to formulate pesticides (Yang et al., 2018, J. Agric.
  • Some plant-care formulations comprising a cross-linked chitosan have been developed for the formulation of plant protecting products by mixing the plant protecting substances with chitosan and inducing cross-linking on the mixture (Vinod et al., 2013, International Journal of Biological Macromolecules, 62(16), 677-683; VinodetaL, 2015, International Journal of Biological Macromolecules, 75 (21), 343-353; Vinod et al, 2016, International Journal of Biological Macromolecules, 64 (31), 6148-6155).
  • TPP tripoly-phosphates
  • the present invention is based on the finding of new use of a chitosan derivative and for the formulation of plant care substances and other agriculturally useful substances.
  • the present invention is based on the unexpected finding of chemically modified chitosan formulations which exhibit strong adherence to plant tissues, allowing targeted application and preventing runoff and/or leaching of plant care products, in particular pesticides. This addresses a major problem as the actual utilization of biological target uptake is only less than 0.1% after dust drift and rainwater leaching (Zhao et al., 2018, J. Agric. Food Chem., 66, 26, 6504 6512; https://doi.org/10.1021/acs.jafc. 7602004).
  • the formulations of the invention are advantageously frost resistant, enable sustained release of PCPs, and degrade very slowly. Further, it has been found that methods of the invention allow to generate in a single step sprayable solution/suspensions of plant care or protecting products (including plant care or protecting products in solid form which are insoluble in water). Finally, the formulations of the invention provide an advantageous protection against biological (e.g. enzymes, microorganisms) or physical (e.g. UV radiation) degradation of PCPs.
  • the present invention also relates to methods of preparation PCPs having the following advantages: capacity to achieve a formulation in water, methods fast and reliable which are versatile and allow to customize formulation types and obtain formulations which are environmentally friendly.
  • An aspect of the invention provides a plant-care formulation comprising a soluble crosslinked chitosan and at least one plant protecting product, said plant care formulation comprises from about 0.01% to about 2 % (w/v) of soluble cross-linked chitosan and uses thereof.
  • Another aspect of the invention provides a method for the preparation of a plant care formulation of the invention.
  • Another aspect of the invention relates to a plant-care formulation obtainable from a method according to the invention.
  • Another aspect of the invention relates to a use of a soluble cross-linked chitosan and at least one plant protecting agent for the preparation of a plant-care formulation.
  • Another aspect of the invention relates to the use of a plant-care formulation according to the invention in agriculture and plant cultivation.
  • Figure 1 shows the appearance of leaf disks (permissive Cabernet Sauvignon leaves) 7 days after inoculation with a suspension of P. viticola sporangia following treatment with various formulations of the invention and comparative formulations as described in Example 2.
  • a water;
  • b copper oxychloride (0.4%);
  • c Formulation of the invention Fl;
  • d Formulation of the invention F2;
  • e grapevine cane extract (7.5 mg/ml);
  • f grapevine cane extract (3.75 mg/ml);
  • g grapevine cane extract (1.875 mg/ml);
  • h Formulation of the invention F3;
  • h Formulation of the invention F4;
  • i Formulation of the invention F5;
  • j copper sulfate (2.5 mg/ml);
  • k copper sulfate (1.25 mg/ml); 1: copper sulfate (0.5 mg/ml);
  • m Formulation of the invention F6;
  • n
  • Figure 2 shows the microscopic appearance of initial copper solutions or suspensions and corresponding copper-containing formulations of the invention observed by microscopy as described in Example 3.
  • a copper sulfate (CuSCU) prior to formulation
  • b formulated copper sulfate
  • c tribasic copper oxychloride (CU2(OH)3C1) prior to formulation
  • d formulated tribasic copper oxychloride
  • e copper hydroxide (Cu(OH)2) prior to formulation
  • f formulated copper hydroxide.
  • Figure 3 shows the microscopic appearance of a colloidal sulfur-containing plant care formulation of the invention observed by electron microscopy as described in Example 4.
  • degree of crosslink means the quantity functional groups converted into crosslinking or grafting bonds relative to the total quantity of functional groups
  • degree of crosslink means the quantity functional groups converted into crosslinking or grafting bonds relative to the total quantity of functional groups initially present on the chitosan, expressed as a percentage.
  • alkyl when used alone or in combination with other terms, comprises a straight or branched chain of C1-C50 alkyl which refers to monovalent alkyl groups having 1 to 50 carbon atoms. This term is exemplified by groups such as methyl, ethyl, n-propyl, i -propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, 1 -ethylpropyl, 2-m ethylbutyl, 3- m ethylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-m ethylpentyl, 3 -methylpentyl, 4- methylpentyl, n-heptyl, 2-methylhexyl, 3 -methylhexyl, 4-methylhexyl, 5 -methylhexyl, n- heptyl,
  • these include C1-C9 alkyl, more preferably Ci-Ce alkyl, especially preferably C1-C4 alkyl, which, by analogy, refers respectively to monovalent alkyl groups having 1 to 9 carbon atoms, monovalent alkyl groups having 1 to 6 carbon atoms and monovalent alkyl groups having 1 to 4 carbon atoms.
  • those include Ci-Ce alkyl.
  • alkenyl when used alone or in combination with other terms, comprises a straight chain or branched C2-C50 alkenyl. It may have any available number of double bonds in any available positions, and the configuration of the double bond may be the (E) or (Z) configuration.
  • This term is exemplified by groups such as vinyl, allyl, isopropenyl, 1 -propenyl, 2 -m ethyl- 1 -propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-l-butenyl, 3- methyl-2-butenyl, 1 -pentenyl, 2-pentenyl, 3 -pentenyl, 4-pentenyl, 4-methyl-3 -pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-heptenyl, 1-octenyl, geranyl, 1-decenyl, 1 -tetradecenyl, 1 -octadecenyl, 9-octadecenyl, 1-eicosenyl, and 3, 7, 11, 15- tetram ethyl- 1
  • these include C2-C8 alkenyl, more preferably C2-C6 alkenyl.
  • C2-C8 alkenyl more preferably C2-C6 alkenyl.
  • aryl refers to an unsaturated aromatic carbocyclic group of from 6 to 14 carbon atoms having a single ring (e.g., phenyl) or multiple condensed rings (c.g, indenyl, naphthyl).
  • Aryl include phenyl, naphthyl, anthryl, phenanthrenyl and the like.
  • Ci-Ce alkyl aryl refers to aryl groups having a Ci-Ce alkyl substituent, including methyl phenyl, ethyl phenyl and the like.
  • aryl Ci-Ce alkyl refers to Ci-Ce alkyl groups having an aryl substituent, including 3-phenylpropanyl, benzyl and the like.
  • heteroaryl refers to a monocyclic heteroaromatic, or a bicyclic or a tricyclic fused-ring heteroaromatic group.
  • heteroaromatic groups include optionally substituted pyridyl, pyrrolyl, pyrimidinyl, furyl, thienyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,3- oxadiazolyl, 1,2,4-oxadia-zolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,3,4-triazinyl, 1,2,3-triazinyl, benzofuryl, [2,3-dihydro]benzofuryl, isobenzofuryl, benzothienyl, benzotriazolyl, isobenzothiazolyl, iso
  • Cs-Cs-cycloalkyl refers to a saturated carbocyclic group of from 3 to 8 carbon atoms having a single ring (e.g., cyclohexyl) or multiple condensed rings (e.g., norbornyl).
  • Cs-Cs-cycloalkyl includes cyclopentyl, cyclohexyl, norbomyl and the like.
  • heterocycloalkyl refers to a Cs-Cs-cycloalkyl group according to the definition above, in which up to 3 carbon atoms are replaced by heteroatoms chosen from the group consisting of O, S, NR, R being defined as hydrogen or methyl.
  • Heterocycloalkyl include azetidinyl, pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, tetrahydrofuranyl and the like.
  • substituted refers to groups substituted with from 1 to 5 substituents selected from the group consisting of “Ci-Ce alkyl,” “C2-C6 alkenyl,” “C2-C6 alkynyl,” “Cs-Cs-cycloalkyl,” “heterocycloalkyl,” “Ci-Ce alkyl aryl,” “Ci-Ce alkyl heteroaryl,” “aryl Ci-Ce alkyl,” “heteroaryl Ci-Ce alkyl,” “Ci-Ce alkyl cycloalkyl,” “Ci-Ce alkyl heterocycloalkyl,” “amino,” “aminosulfonyl,” “ammonium,” “acyl amino,” “amino carbonyl,” “aryl,” “heteroaryl,” “sulfinyl,” “sulfonyl,” “alkoxy,” “alkoxy carbonyl,” “c
  • biologically acceptable refers to a carrier comprised of a material that is not biologically or otherwise undesirable and not especially toxic.
  • carrier refers to any component present in a formulation other than the active agent and thus includes diluents, binders, lubricants, disintegrants, fillers, coloring agents, wetting or emulsifying agents, pH buffering agents, preservatives and the like.
  • plant protecting products refers to products intended for use in agriculture or in plant growing processes, said products consisting of, or containing substances active as plant safeners or synergists.
  • Such products or substances are useful for protecting plants against all harmful organisms or preventing the action of such organisms (e.g. fungicides, insecticides, bactericides), for influencing the life processes of plants, such as substances influencing their growth, such as fertilizers or preserving plant products (e.g. extending the life of cut flowers), for aiding in recovery after injuries or abiotic stress (e.g. frost damage), for controlling or preventing undesired growth of plants or for destroying undesired plants or parts of plants (e.g.
  • PCPs plant protecting products
  • plant protecting substances refers to products intended for use in agriculture or in plant growing processes, said products consisting of, or containing substances active as plant safeners or synergists.
  • Such products or substances are useful for protecting plants against all harmful organisms or preventing the action of such organisms (e.
  • PCPs include small molecules, synthetic analogs of DNA and RNA oligonucleotides, low-molecular weight compounds of biological origin: hydrophobic compounds, such as terpenoids and pyrethroids, and others and hydrophilic extracts, such as extracts of polyphenols, polysaccharides, high-molecular weight substances of biological origin: proteins (such as Delta endotoxins from Bacillus thuringiensis) and nucleic acids (such as anti-sense DNA and RNA oligonucleotides), biological entities such as spores, bacteria and other microorganisms such as viruses and multicellular organisms (e.g. nematodes and insects).
  • hydrophobic compounds such as terpenoids and pyrethroids
  • hydrophilic extracts such as extracts of polyphenols, polysaccharides, high-molecular weight substances of biological origin: proteins (such as Delta endotoxins from Bacillus thuringiensis) and nucleic acids (such as anti-sense DNA and
  • plant protecting products or “plant protecting substances” comprises agents also referred to as plant protecting products (PPP) and substances which are also referred to under the generic term “pesticides”.
  • PPP plant protecting products
  • pesticides pesticides
  • Chemical fungicides Inhibitors of nucleic acid metabolism: phenylamides (acylalanines, oxazolidinones, butyrolactones), hydroxy-(2-amino-) pyrimidines, heteroaromatics (isoxazoles, isthiazolones), carboxylic acids; Inhibitors of cell division: methyl benzimidazole carbamates (benzimidazoles, thiophanates), N-phenyl carbamates, benzamides, thiazole carboxamide, phenylureas, cyanoacrylates, aryl-phenyl-ketones; Inhibitors of respiration: succinate-dehydrogenase inhibitors (phenyl-benzamides, phenyl-oxo-ethyl thiophene amide, pyridinyl-ethyl-benzamides, phenyl-cyclobutyl- pyridineamide, furan- carboxamides, oxa
  • This class further includes chemical fungicides belonging to the class of cyanoacetamide-oximes, phthalamic acids, benzotriazines, benzene-sulphonamide, pyridazinone, phenyl-acetamide, guanidines, cyano-methylene-thiazolidine, 4-quinolyl-acetates, tetrazolyloximes, glucopyranosyl antibiotics and copper (different salts), sulphur, dithio-carbamates and relatives, phthalimides, chloronitriles, sulfamides, bis-guanidines, triazines, quinones, quinoxalines, maleimide, thiocarbamate.
  • chemical fungicides belonging to the class of cyanoacetamide-oximes, phthalamic acids, benzotriazines, benzene-sulphonamide, pyridazinone, phenyl-acetamide, guanidines, cyano
  • FRAC Code List 2021 Fungal control agents sorted by cross resistance pattern and mode of action https://www.frac.info/docs/default-source/publications/frac-code-list/frac-code-list- 2021— final.pdf
  • Biological fungicides Inhibitors of lipid transport/membrane biosynthesis and metabolism: Bacillus amyloliquefaciens. Melaleuca allernifolia. plant oils (eugenol, geraniol, thymol), amphoteric macrolide from Streptomyces natalensis!
  • Streptomyces chattanoogensi Host plant defene induction: polysaccharides (chitosan and others), plant extracts (anthraquinones, resveratrol), Bacillus spp., Saccharomyces spp.; Multiple modes of action: plant extracts (lectin, phenols, sesquiterpenes, triterpenoids, coumarins, terpene hydrocarbons, terpene alcohols, terpene phenols) such as grapevine cane extracts, living microbes or extract, metabolites (Trichoderma spp., Clonostachys spp., Coniothyrium spp., Saccharomyces spp., Bacillus spp., Pseudomonas spp., Streptomyces spp.). Further possible agents are referred to in Fungicide Resistance Action Committee (FRAC): FRAC Code List 2021, supra,'
  • acetylcholinesterase inhibitors (carbamate, organophosphates), GABA-gated chloride channel blockers (cyclodiene organochlorines, phenylpyrazoles), sodium channel modulators (pyrethroids, pyrethrins, DDT, ethoxychlor), nicotinic acetylcholine receptor (nAChR) modulators (neonicotinoids, nicotine, sulfoximines, butenolides, mesoionics, spinosyns), Glutamate- gated chloride channel (GluCl) modulators (avermectins, milbemycins), chordotonal organ TRPV channelmodulators (pyridine azomethine derivatives, pyropenes, nereistoxin analogues, amitraz, oxadiazines, semicarbazones, diamides, flonicamid, meta-diamides Is
  • This class further includes chemical insecticides belonging to the class of azadirachtin, benzoximate, bromopropylate, chinomethionat, dicofol, lime sulfur, mancozeb, pyridalyl, sulfur;
  • Antisense oligonucleotides analogs modified bases
  • Biological Insecticides Microbial disruptors of midgut membranes: Bacillus thuringiensis and the insecticidal proteins they produce (Cry), Bacillus sphaericus, Paenibacillus popillia, Serratia entomophilia, Host-specific occluded pathogenic viruses: Granuloviruses, Nucleopolyhedroviruses, Reoviridae, Parvoviridae, Nudiviruses and GS-omega/kappa HXTXHvla peptide Further possible agents are referred to in Insecticide Resistance Action Committee, 2020, supra.
  • This class further includes biological Insecticides belonging to the class of Burkholderia spp, Wolbachia pipientis, Chenopodium ambrosioides near ambrosioides extract, fatty acid monoesters with glycerol or propanediol, Neem oil, Beauveria bassiana, Metarhizium anisopliae, Paecilomyces fumosoroseus;
  • Entomopathogenic fungi (Litwin et al., 2020, Rev Environ Sci Biotechnol, 19, 23 42) Insecticidal nematodes ; Earth and minerals: diatomaceous earth, silicates; chemical herbicides: Inhibitors of Photosynthesis: triazines, triazinones, uracils, phenylcarbamates, amides, nitriles, n-phenyl-imides, diphenyl ethers, n-phenyl- oxadiazolones, n-phenyl-triazolinones, pyridiniums, phosphinic acids, cyclopyrimorat, triketones, pyrazoles, phenyl -ethers, n-phenyl heterocycles, diphenyl heterocycles, Isoxazolidinones, amitrole; Inhibitors of cellular metabolism: imidazolinone, sulfonylurea
  • the chitosan derivative suitable for a use according to the invention is a soluble crosslinked chitosan as described in PCT/EP2021/053204 (WO 2021/160667) or any pharmaceutically acceptable salts thereof.
  • the cross-linked chitosan is obtainable by a method comprising the following steps: a) providing a chitosan and leaving the said chitosan to swell in a solvent; b) acylating the amino groups of said chitosan with an acrylic compound of Formula (I): wherein Ri is an a halogen or any other leaving group that upon removal, ensures acylation of an amino group such as 3 -hydroxybenzotriazole ester, anhydride (including mixed anhydrides), N-hydroxysuccinimide, pentachlorophenol, 2-nitro-4-sulfophenol esters and other similar leaving groups; R2, R3 and R4 are independently selected from H; optionally substituted alkyl (e.g.
  • Ci-Ce alkyl optionally substituted alkenyl (e.g. C2-C6 alkenyl), optionally substituted alkynyl (e.g. C3-C6 alkynyl), optionally substituted cycloalkyl (e.g. Cs-Cs-cycloalkyl), optionally substituted cycloalkenyl (e.g. C4-C8 cycloalkenyl), optionally substituted cycloalkynyl (e.g. Cs-Cs cycloalkynyl), optionally substituted heterocycloalkyl; optionally substituted aryl (e.g.
  • the solvent used under step a) and/or b) is a protic solvent (such as alcohols or water).
  • the free acrylic acids which are formed if a protic solvent such as alcohols or water
  • a protic solvent such as alcohols or water
  • the solvent is an aprotic solvent, in particular under step a) and/or b) and/or c).
  • step c) if an aprotic solvent is used under step c) if no further step f) of subsequent acylation is carried out.
  • step a) is conducted at room temperature.
  • the R3 or R4 but also R2 groups of the acylated product of step b) will react with the primary amino groups of the glucosamine backbone to form a cross-link between glucosamines.
  • the groups reacting will depend on the specific acrylic compound. For example, for acrylic and methacrylic acids, the groups reacting with the primary amino groups of the glucosamine backbone are groups R3 or R4. However, when R3 and R4 groups are replaced by halogen atoms, then R2 groups will react with the primary amino groups of the glucosamine backbone.
  • the soluble cross-linked chitosan is fully soluble at pH ⁇ 5.5 in aqueous solution.
  • the soluble cross-linked chitosan has a viscosity that is approximately 3-fold inferior to the original chitosan that was used for its synthesis.
  • the working concentrations range from 0.01% to 2%.
  • this cross-linking leads to the formation of nanoparticles.
  • the soluble cross-linked chitosan forms a nanosuspension, typically particles having a diameter from about 5 nm to about 50 nm (e.g. 20 nm) at pH 7.0 or above.
  • a nanosuspension has a lower viscosity than the corresponding solution (at pH ⁇ 7.0) and can be manipulated as a true solution. In case of any precipitate/sediment formation, it can be easily resuspended.
  • the soluble cross-linked chitosan can be obtained by a method schematized under Scheme 1 as follows: wherein a chitosan (A) wherein m is a integer comprised between 1 and 12’500 and n is a integer comprised between 1 and 12’500, is first provided in a swollen state in an aprotic solvent at room temperature and then the amino groups of said chitosan are acylated with an acrylic compound (I) and the resulting acylation product (Bl) is then reacted in presence of a base to lead to a cross-linked chitosan (B2) which can then be isolated by purification to lead to a purified cross-linked chitosan according to the invention.
  • A chitosan
  • n is a integer comprised between 1 and 12’500
  • the chitosan can be provided in swollen state, even in dissolved state, in a protic solvent but in this case, side reactions of hydrolysis of the acylating agent can occur and this must be taken into account when calculating reaction loads. Additionally, in this case, it will be necessary to wash the acylated chitosan obtained under step b) to remove the hydrolysis products of the acylating agent before the stage of aza-Michael reaction under step c).
  • the chitosan is provided in absence of water and the acylating step is carried out in absence of water.
  • the absence of water advantageously leads to higher yields and avoid the formation of side products.
  • the acylation step is conducted in absence of water.
  • an aprotic solvent can be used as reaction medium or a supercritical fluid.
  • the aprotic solvent is a polar aprotic solvent such as for example selected from DMF and DMSO.
  • a supercritical fluid can be a supercritical solvent such as carbon dioxide, nitric oxide (I), freons (chloro(bromo)(fluoro)hydrocarbons) which is used to provide the acylating agent to the reaction medium and then acylation reaction carried out after removal of the supercritical solvent from the reaction medium, for example by lowering the pressure below the critical value.
  • the acylation step is conducted an anhydrous aprotic medium.
  • a polar aprotic solvent is selected from dimethylformamide (DMF), dimethylacetamide, acetonitrile (MeCN), N- methylpyrrolidone, dimethyl sulfoxide (DMSO) or a mixture thereof.
  • di chloromethane, di chloroethane, chloroform, and other chloro(fluoro)hydrocarbons can be also used as a polar aprotic solvent, but when conducting the aza-Michael reaction step c), those solvents should be distilled off right before the provision of the base. It is desirable to perform such distillation at temperatures not exceeding 60°C, which is feasible at atmospheric pressure for most of the mentioned solvents. If a high-boiling solvent was used, distillation must be carried out under reduced pressure.
  • ethers and esters, ketones can also be used as solvents for the reaction steps a) to c) under anhydrous conditions but reactions in such solvents will proceed more slowly.
  • diethyl ether diisopropyl ether, methyl tert-butyl ether, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone and diethyl ketone can be used.
  • the acylation step b) can be conducted by any method described in the context of acylation of glucosamine with acryloyl chloride (Zhang et al., 2017, Biomacromolecules, 1, 3, 778 786; Bu et al., 2017, Advances, 7, 76, 48166 -
  • acylation methods using carbodiimide with the formation of intermediate enol esters can be used under step b) (WO 2019/60740; Hao-Bin et al, 2018, Carbohydrate Polymers, 196, 359 - 367).
  • DCC N,N'-dicyclohexylcarbodiimide
  • l-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride and N-cyclohexyl-N'-(2-morpholinoethyl)carbodiimide methyl p-toluenesulfonate CAS Registry Number: 2491-17-0
  • step b) Known acylation methods using azides can be used under step b) (Honzl et al, 1961, Coll. Czech. Chem. Commun., 26, N. 9, 2333-2344).
  • acylation methods using mixed anhydrides can be used under step b) (Wieland et al., 1951, Ann. Chem., 572, N3, 190-194; Belleau et al., 1968, J. Amer. Chem. Soc., 90, N 6, 1651-1652; Gorecka et al., 1978, Synthesis, N 6, 474-476; Diago-Meseguer et al., 1980, Synthesis, N 7, 547-551; Leplawy et al., 1960, Tetrahedron, 11, N 1, 39-51).
  • the use of internal anhydrides is also possible for acylation, for example maleic anhydride (Liwschitz et al.
  • acylation methods using activated esters through the formation of activated amides can be used under step b) such as a carbonyldiimidazole method (Paul etal., 1960, J. Amer. Chem. Soc., 82, N 17., 4596-4600), a cyanomethyl ester method (Schwyzer et al., 1955, Helv. Chim. Acta, 38, N 1, 80-83), a thiophenyl ester method (Wieland et al., 1951, supra), a substituted phenyl ester method (Gross et al. , 1983, Mayenhofer, editors. Moscow: Mir., P.
  • acylation methods can be can be used under step b) such as ketenimine method (Stevens et al., 1958, J. Amer. Soc., 80, N 15, 4069-4071); Acetylene derivatives method (Arens, 1955, Rec. Trav. Chim., 74, N 6, 759-770; Gais 1978, Aktivtechnischsstoff fur Peptidsynthesen J. Angew. Chem. Int. Ed, 90(8), 625-626 https://d0i.0rg/l 0.1002/ange.19780900808); method using derivatives of cyanamide (Losse et al, 1960, Ann.
  • the acrylic compound of Formula (I) can be an acid, an acid halide, an active ester (e.g. 3 -hydroxybenzotriazole ester, N- hydroxysuccinimide, pentachlorophenol, 2-nitro-4-sulfophenol esters and esters having other similar leaving groups), an anhydride or mixtures thereof.
  • an active ester e.g. 3 -hydroxybenzotriazole ester, N- hydroxysuccinimide, pentachlorophenol, 2-nitro-4-sulfophenol esters and esters having other similar leaving groups
  • a soluble cross-linked chitosan suitable according to the invention can be identified be a method comprising the steps of: providing a chitosan to be characterized in a solvent (e.g. methylene chloride or chloroform); acylating said chitosan as described herein (e.g. as acetyl chloride or acetic anhydride) under vigorous stirring such as for about 0°C to about 20°C, such as about 30 minutes; neutralizing the reaction medium with a base (e.g. diisopropylethylamine as non- nucleophilic base); evaporating the solvents and washing the obtained neutralized product; subjecting the product to a reflux acid hydrolysis (e.g.
  • a solvent e.g. methylene chloride or chloroform
  • acylating said chitosan as described herein e.g. as acetyl chloride or acetic anhydride
  • a base e.g. diisopropyle
  • said soluble cross-linked chitosan and formulations thereof according to the invention differ from standard chitosans in that it generates not a viscous gel, but a low-viscosity solution (e.g. for relatively low concentrations (up to 2% [w/v]) NovochizolTM is 3 times less viscous than chitosan) that can be applied to any surface (seed, foliage) as a very fine aerosol.
  • a low-viscosity solution e.g. for relatively low concentrations (up to 2% [w/v]
  • This property enables to formulate all classes of plant protecting substance or a mixture thereof: small molecules, peptides, proteins, nucleic acids, and supram olecular entities such as inanimate particles, viruses, cells, and multicellular organisms.
  • the soluble cross-linked chitosan acts as an emulsifier for very hydrophobic plant protecting substances that are otherwise very difficult to formulate.
  • the soluble cross-linked chitosan allows to prepare plancare formulations with customizable sustained release properties.
  • a plant care formulation wherein said formulation is a liquid formulation.
  • a plant care formulation wherein said formulation is a solid formulation.
  • a plant-care formulation comprising from about 0.05% to about 1% (w/v) (e.g. from about 0.06% to about 0.15% (w/v)) of a soluble cross-linked chitosan and at least one plant protecting product, wherein said soluble cross-linked chitosan is fully soluble at pH ⁇ 5.5 in aqueous solution.
  • a plant care formulation wherein said formulation contains from about 0.0001% to about 99.99% (w/v) of at least one plant protecting product/sub stance.
  • a plant care formulation wherein said formulation may further contain any further biologically acceptable carrier.
  • a plant care formulation wherein the mass ratio plant protecting substance: soluble cross-linked chitosan is between 0.00001: 1 to 10’000: 1.
  • a plant care formulation wherein mass ratio plant protecting substance: soluble cross-linked chitosan is between 0.5: 1 to 10’000: 1.
  • a plant care formulation wherein said at least one plant protecting product is selected from a biological and a chemical fungicide.
  • a plant care formulation wherein said at least one plant protecting product is selected from a plant extract (e.g. grapevine cane extracts) and copper salt or oxide.
  • a plant extract e.g. grapevine cane extracts
  • copper salt or oxide e.g. copper salt or oxide
  • a plant care formulation wherein said at least one plant protecting product is a semiochemical or a mixture of semi ochemi cals such as pheromones (e.g. gall midge sex pheromones, straight-chained lepidopteran pheromones, mite pheromones and the like) and allochemics (e.g. allomones, kairomones or synomones).
  • pheromones e.g. gall midge sex pheromones, straight-chained lepidopteran pheromones, mite pheromones and the like
  • allochemics e.g. allomones, kairomones or synomones.
  • a plant care formulation according to the invention wherein said at least one plant protecting product is grapevine cane extract and the ratio (w/w) grapevine cane extract to soluble cross-linked chitosan is from 10: 1 to 1 : 100.
  • a plant care formulation according to the invention wherein said at least one plant protecting product is copper salt or oxide and the ratio (w/w) copper salt or oxide to cross-linked chitosan is from 10: 1 to 1 : 100.
  • a plant care formulation according to the invention wherein said at least one plant protecting product is copper salt or oxide and the ratio (w/w) copper salt or oxide to cross-linked chitosan is from 3 : 1 and 10: 1.
  • a plant care formulation according to the invention wherein said at least one plant protecting product is a semiochemical or a mixture of semi ochemi cals such as pheromones and the ratio (w/w) pheromone to cross-linked chitosan is from 100: 1 to 1 000 000: 1.
  • a method for the preparation of a plant-care formulation comprising a step of combining at least one plant protecting substance or a mixture thereof with a soluble cross-linked chitosan (e.g. at 0.01% and 2% (w/v)).
  • the method is carried out at a temperature between 0°C and 100°C under atmospheric pressure and between 0°C and 374°C under 21.8MPa.
  • the maximum allowable temperature is 374°C, under 21.8 MPa and the maximum allowable pressure 1’000 MPa.
  • the temperature of the mixture needs to be uniform and therefore should be carried out by adequate heating methods ensuring such a uniform heating of the mixture during mixing step for example by the use of microwave, infra-red or terahertz radiation heating methods.
  • the plant care formulation is a liquid formulation.
  • a method for the preparation of a plant-care formulation comprises the steps of:
  • a soluble cross-linked chitosan in aqueous solution e.g. at 0.01% and 2% (w/v)
  • vigorous mixing such as under ultrasound sonication.
  • the soluble cross-linked chitosan is added to the mixture such that mass ratio plant protecting substance: soluble cross-linked chitosan is between 0.00001 :1 to 10’000: 1.
  • the soluble cross-linked chitosan is added to the mixture such that mass ratio plant protecting substance: soluble cross-linked chitosan is between 0.5: 1 to 10’000: 1.
  • mass ratio plant protecting substance: soluble cross-linked chitosan is between 0.5: 1 to 10’000: 1.
  • a micro-emulsion of cross-linked chitosan is obtained and the plant protecting substance aggregates (pm) are coated with cross-linked chitosan.
  • the soluble cross-linked chitosan is added to the mixture such that mass ratio plant protecting substance: soluble cross-linked chitosan is between 0.00001 : 1 to 0.5: 1.
  • the cross-linked chitosan will be impregnated with the plant protecting substance.
  • a solution of a plant protecting substance can be prepared such as in methanol, ethanol, acetone, DMF, DMSO, N-Methyl-2 -Pyrrolidone, acetic acid.
  • a typical solution may comprise 90% (w/v) plant protecting substance and 10% (w/v) solvent, but minimal amounts of solvent (e.g. down to 0.01% w/v.) may be used.
  • plant protecting substance concentrations as low as 0.001% (w/v) may be used (for example, for derivatives of glycyrrhizinic acid).
  • Plant protecting substances existing in liquid form may be used as such or diluted in a solvent of choice.
  • the water-miscible solvent used to introduce the plant protecting substance into the formulation may be removed immediately after formulation by distillation at atmospheric pressure, or at a higher pressure so as to increase the temperature to accelerate solvent elimination process and increase the solubility of the plant protecting substance.
  • the solvent may be removed through dialysis, freezing or barbotage. Unless it is desirable to concentrate the solution, water may be added to the mixture during or after the removal of the solvent to compensate for the loss of volume.
  • the method comprises the steps of:
  • aqueous solution of a soluble cross-linked chitosan e.g. at 0.01% and 2% (w/v)
  • the liquid mixture between the soluble cross-linked chitosan and the plant protecting substance can be used readily or further subjected to drying or freeze-drying step for storage purposes before use.
  • drying or freeze-drying step for storage purposes before use.
  • a number of drying techniques may be used such as spray drying, lyophilization with or without auxiliary substances, drying in a rotary or film evaporator, under atmospheric or reduced pressure. It is also possible to freeze the preparation for storage purposes.
  • a method for the preparation of a plant-care formulation according to the invention wherein the plant protecting substance is combined with a soluble cross-linked chitosan (e.g. at 0.001% and 25% (w/v.)) in solid state wherein one at least one of the two combined agent is in solid state.
  • a soluble cross-linked chitosan e.g. at 0.001% and 25% (w/v.)
  • the obtained powder or suspension mixture may then be dissolved in water to obtain a plant-care formulation and used immediately or frozen for storage.
  • a plant protecting substance when the plant protecting substance is insoluble or poorly soluble, is provided method for the preparation of a plant-care formulation, said method comprising the steps of: providing a plant protecting substance in solid form (e.g. as a fine powder of particles having a diameter from about 5 nm to about 200 pm); adding an aqueous solution of a soluble cross-linked chitosan (e.g. at 0.01% and 2% (w/v)) to the plant protecting substance in solid form under vigorous mixing such as under ultrasound sonication or spraying.
  • a plant protecting substance in solid form e.g. as a fine powder of particles having a diameter from about 5 nm to about 200 pm
  • an aqueous solution of a soluble cross-linked chitosan e.g. at 0.01% and 2% (w/v)
  • a plant-care formulation comprising the steps of: providing a soluble cross-linked chitosan (e.g. at 0.01% and 2% (w/v)) or a salt thereof, in dry state; mixing a plant protecting substance in solid form (e.g. as a fine powder of particles having a diameter from about 5 nm to about 200 pm);
  • the obtained powder or suspension mixture may then be dissolved/diluted in water with addition of acids with or without additional heating.
  • the solid particles of the cross-linked chitosan and of the plant protecting substance may either be applied directly to the plant by spraying or the sprayed particles may be dried, frozen or dissolved/resuspended in water or another compatible solvent (e.g. glycerin, propylene glycol, ethanol, N-Methyl-2 -Pyrrolidone, etc.).
  • a compatible solvent e.g. glycerin, propylene glycol, ethanol, N-Methyl-2 -Pyrrolidone, etc.
  • the plant protecting substance solution or suspension may be prepared in a buffer solution to maintain the pH environment of the acid-labile plant protecting substance in a range where the plant protecting substance is not degraded (pH 6.5 - 7.5).
  • the plant-care formulation of the invention may further include other biologically acceptable ingredients such as salts, oxides, hydroxides, urea, melamine, sugars, polysaccharides, antioxidants, natural and synthetic (polymeric) emulsifiers and synthetic organic chemicals commonly used for plant-care formulations.
  • Those biologically acceptable ingredients may serve different purposes: such as anti-caking agents in case of solid formulations, as anti-oxidants, as antipartitioning agents, as cryoprotectors, as enhancing excipients, as pH buffers, as rheological additives that improve the conditions for product application, as dyes or odorants for the purpose of detecting treated surfaces.
  • the plant-care formulation according to the invention may be applied to seeds (e.g. by drying an aerosol formulation) to maintain a low degree of humidity (e.g. as little as for example 8%) which is particularly advantageous to in case of seed treatment, as it is important to prevent premature germination.
  • a low degree of humidity e.g. as little as for example 8%
  • the plant-care formulation obtained by a method according to the invention may then be further mixed with the soluble crosslinked chitosan, typically at a ration from about 0.5: 1 to about 10’000: 1 to create an extra layer on the plant-care formulation particles which may increase adherence to the plant parts.
  • this extra layer is monolayer, i.e. about 20 nm thick and contributes to delay the release of the plant protecting care/product and to a better adherence to plant tissue.
  • DMEM Dulbecco's Modified Eagle Medium
  • Example 1 Preparation of plant care formulation of the invention having fungicidal properties
  • a plant care formulation of the invention comprising a chemical fungicide was prepared according to a method of the invention and tested on Spring wheat, variety Thasos (Strube) (39.8 g/1000 seeds) as compared to commercial formulations as follows. Each experiment comprised 6 groups:
  • Seeds were treated under humidification (10 1/t) in closed plastic containers as described below. a) Assessment of the phytosanitary state of the treated seeds
  • the phytosanitary state of the treated seeds was assessed by the evaluation of the degree of infection, growth and development of sprouted seedlings.
  • degree of infection determined visually by counting the number of lesions per seedling
  • visual assessment the number of seedlings with lesions in the root system
  • height of the seedlings determined visually
  • number of roots per seedling determined visually
  • the length of the tap root determined visually
  • dry biomass of the seedlings The results are presented under Tables 1 and 2 below where the biological efficacy represents the proportion of seedlings without lesions.
  • plant-care formulation of the invention allows to substantially decrease the amounts of difenoconazole and cyproconazol, without affecting efficacy as compared to a commercial preparation.
  • Example 2 Preparation of plant care formulation of the invention for grapevine treatment against Plasmapora viticola
  • a plant care formulation of the invention was prepared with following ingredients: - 1% w/v soluble cross-linked chitosan (NovochizolTM) + 0.5% succinic acid aqueous solution: 1 (soluble cross-linked chitosan in aqueous solution); - 1% (w/v) regular chitosan + 0.5% succinic acid solution, 2 (regular chitosan in suspension in aqueous solution);
  • soluble chitosan NovochizolTM
  • soluble cross-linked chitosan in aqueous solution 20 ml NovochizolTM solution + one plant protecting substance in a water-miscible solvent: 20 ml regular chitosan solution (final concentrations: 0.5% or 5 mg/ml NovochizolTM, 0.5% or 5 mg/ml regular chitosan);
  • Example 3 Reduced-copper plant care formulation of the invention for grapevine treatment against Plasmapora viticola
  • Copper-based antimicrobial compounds are widely used in both conventional and organic agriculture, and are the most effective contact fungicides against Plasmapora viticola, in grapevine (Koledenkova et al., 2022, Front Microbiol., 11, 13, 889472. https://doi.org/10.3389/fmicb).
  • their extensive use over the last 150 years is problematic, as copper is accumulating in the top soils, with deleterious effects on soil biota and toxicity. (Lamichhane et al., 2018, Agron. Sustain. Dev., 38, 28, https://doi.org/!
  • Plant care formulations of the invention were prepared as follows:
  • CU2(OH)3C1 (7.246 g, fine powder) were added to 500 ml deionized water and 500 ml of Novochizol 20X concentrate solution were added at a rate of 15 ml/min, under vigorous active mixing (ultrasound homogenization using a 2000W probe sonicator).
  • CU2(OH)3C1 (5.414 g, fine powder) were dissolved in deionized water to 500 ml and 500 ml of 3% w/v Novochizol 20X concentrate solution were added at a rate of 15 ml/min, under vigorous active mixing (ultrasound homogenization using a 2000W probe sonicator).
  • CU2(OH)3C1 (5.414 g, fine powder) were dissolved in deionized water to 500 ml and 500 ml of 3% w/v Novochizol 20X concentrate solution were added at a rate of 15 ml/min, under vigorous active mixing (ultrasound homogenization using a 2000W probe sonicator).
  • plants Upon inoculation, plants were placed in an environment to induce sporulation (24h at 100% relative humidity and 21 °C, light 16h day/8h night) and then transferred to a growth chamber for disease development (20°C; light regime: 16h day/8h night) for a period of 6 days. Disease incidence was assessed as the proportion (%) of leaves with disease symptoms and disease severity as the proportion (%) of diseased leaf surface.
  • Adherence of formulations (Wash-off, Table 6) were assessed by spraying treated seedlings in a spray cabinet with water, as above, for 20 seconds, ’A day after initial treatment and letting the seedlings dry as above prior to inoculation.
  • Plant-care formulations of the invention provides a sustained release of the plant protecting product, a better adherence to plant tissues, a certain synergy between chitosan’s plant growth and immune defense elicitor effects and the plant protecting product.
  • Example 4 Novel colloidal sulfur-containing plant care formulation of the invention for wheat treatment against Alternaria triticina and Puccinia triticina
  • Soluble cross-linked chitosan (20 g) was dissolved in 1 liter tartric acid aqueous solution (7.5% w/v) and added at a rate of 15 ml/min to sodium thiosulfate pentahydrate (413, 5 g) dissolved to 800 ml deionized water, under vigorous active mixing (ultrasound homogenization using a 2000W probe sonicator).
  • the resulting formulation contained approx. 69 grams of colloidal, elemental sulfur per liter in a 1.1% soluble cross-linked chitosan solution.
  • the resulting formulation was added to 1.8 liter 3% Novochizol (w/v) in 1.5% succinic acid (w/v), under vigorous active mixing (ultrasound homogenization using a 2000W probe sonicator).
  • the final, double formulation containing approx. 34.5 grams of colloidal, elemental sulfur per liter in a 2% (w/v) soluble cross-linked chitosan solution was diluted to yield various concentrations of working colloidal sulfur-containing plant care formulation.
  • a colloidal sulfur-containing plant care formulation of the invention consists of very fine (20 nm) sulfur particles, a characteristic of interest for a contact fungicide (Fig. 3).
  • the formulation acts as an effective plant protection product against Alternaria triticina and Puccinia triticina, resulting in a significant increase in harvest.

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Abstract

La présente invention concerne des formulations pour le soin de plantes, comprenant des produits phytosanitaires (PPP) et des substances utiles dans l'agriculture et la croissance des plantes, ainsi que leurs procédés de préparation.
PCT/EP2022/072081 2021-08-06 2022-08-05 Compositions pour le soin de plantes et leurs utilisations Ceased WO2023012332A1 (fr)

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WO2024153800A1 (fr) * 2023-01-20 2024-07-25 Universität Münster Compositions de traitement de plantes comprenant des émulsions enrobées de chitosane
WO2025182713A1 (fr) * 2024-02-28 2025-09-04 三洋化成工業株式会社 Auxiliaire de croissance de plante et procédé de culture de plante

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024153800A1 (fr) * 2023-01-20 2024-07-25 Universität Münster Compositions de traitement de plantes comprenant des émulsions enrobées de chitosane
WO2025182713A1 (fr) * 2024-02-28 2025-09-04 三洋化成工業株式会社 Auxiliaire de croissance de plante et procédé de culture de plante

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