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WO2025117659A1 - Insecticide delivery by nanocarriers - Google Patents

Insecticide delivery by nanocarriers Download PDF

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Publication number
WO2025117659A1
WO2025117659A1 PCT/US2024/057643 US2024057643W WO2025117659A1 WO 2025117659 A1 WO2025117659 A1 WO 2025117659A1 US 2024057643 W US2024057643 W US 2024057643W WO 2025117659 A1 WO2025117659 A1 WO 2025117659A1
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WO
WIPO (PCT)
Prior art keywords
conjugate
methyl
spp
phenyl
insecticide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/057643
Other languages
French (fr)
Inventor
Juan Pablo Giraldo Gomez
Sandeep Sharma
Thomas M. PERRING
Ysabel GIRALDO
Wen Xu
Huazhang Huang
Emir ISLAMOVIC
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Corp
University of California Berkeley
University of California San Diego UCSD
Original Assignee
BASF Corp
University of California Berkeley
University of California San Diego UCSD
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Filing date
Publication date
Application filed by BASF Corp, University of California Berkeley, University of California San Diego UCSD filed Critical BASF Corp
Publication of WO2025117659A1 publication Critical patent/WO2025117659A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • A01N25/12—Powders or granules
    • 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
    • A01P5/00—Nematocides
    • 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
    • A01P7/00—Arthropodicides
    • 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
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • 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
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides

Definitions

  • the disclosure relates to cyclodextrin-modified nanomaterials for carrying insecticides that release such insecticides under controlled conditions.
  • the disclosure also relates to methods of delivering insecticides to a plant and treating an insect infestation on the plant by introducing cyclodextrin-modified nanomaterials carrying the insecticides to the plant.
  • the disclosure provides a conjugate comprising a cyclodextrin conjugated to a nanoparticle, wherein the cyclodextrin comprises a pesticide, optionally an insecticide.
  • the pesticide is an insecticide.
  • the nanoparticle is a quantum dot, carbon dot, carbon nanotube, silica nanoparticle, lipid nanoparticle, liposome, metal nanoparticle, metal oxide nanoparticle, or a combination thereof.
  • the nanoparticle is a carbon dot.
  • the nanoparticle has an average size of between about 1 nm and 100 nm.
  • the nanoparticle can have an average size of between about 1 nm and 50 nm, 20 nm and 80 nm, 40 nm and 60 nm, or 75 nm and 95 nm in size.
  • the nanoparticle can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53,
  • the nanoparticle has a size of between about 1 nm and 100 nm.
  • the nanoparticle can have a size of between about 1 nm and 50 nm, 20 nm and 80 nm, 40 nm and 60 nm, or 75 nm and 95 nm in size.
  • the nanoparticle can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,
  • the nanoparticle has an average size of between about 1 and 8 nm, 2 and 9 nm, 5 and 7 nm, 4 and 8 nm, or 3 and 9 nm.
  • the nanoparticle can have a size of between about 1 and 8 nm, 2 and 9 nm, 5 and 7 nm, 4 and 8 nm, or 3 and 9 nm.
  • the nanoparticle has an average size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm.
  • the nanoparticle can have a size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm.
  • the conjugate has an average size of between about 1 nm and 100 nm.
  • the conjugate can have a size of between about 1 nm and 50 nm, 20 nm and 80 nm, 40 nm and 60 nm, or 75 nm and 95 nm in size.
  • the conjugate can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57,
  • the conjugate has an average size of between about 1 and 8 nm
  • the conjugate can have a size of between about 1 and 8 nm, 2 and 9 nm, 5 and 7 nm, 4 and 8 nm, or 3 and 9 nm.
  • the conjugate has an average size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm.
  • the conjugate can have a size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm.
  • the cyclodextrin is gamma cyclodextrin.
  • the cyclodextrin can be a beta-cyclodextrin.
  • the cyclodextrin can be an alpha-cyclodextrin.
  • the conjugate comprises between about 1-5 cyclodextrins conjugate to a nanoparticle.
  • the conjugate comprises about 3 cyclodextrins conjugate to a nanoparticle.
  • the cyclodextrin forms a molecular cage and the pesticide, optionally an insecticide, is inside the molecular cage.
  • the insecticide is an AChE inhibitors.
  • the AChE inhibitor is aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifosmethyl, coumaphos, cyanophos, demeton-S
  • the insecticide is a GABA-gated chloride channel antagonist.
  • the GABA-gated chloride channel antagonist is a cyclodiene organochlorine compound, endosulfan, chlordane, phenylpyrazoles, optionally ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole, or a combination thereof.
  • the insecticide is a sodium channel modulator.
  • the sodium channel modulator is a pyrethroid, optionally acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bio-resmethrin, cycloprothrin, cyfluthrin, beta- cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate
  • the insecticide is a nAChR agonist.
  • the nAChR agonist is a neonicotinoid, acetamiprid, clothianidin, cycloxaprid, dinotefuran, im-idacloprid, nitenpyram, thiacloprid, thiamethoxam; 4,5-dihydro- N-nitro-l-(2-oxiranylmethyl)-lH-imidazol-2-amine, (2E-)-l-[(6-Chloropyridin-3-yl)methyl]- N'-nitro-2-pentylidene _, hydrazine _, carbox _, imidamide; l-[(6-Chloropyridin-3-yl)methyl]-7- methyl-8-nitro-5-propoxy-l,2,3,5,6,7-hexahydro _, imidazo[l,2-a]pyridine; nicotine; sulfoxaflor; flupyradifurone; triflumezo
  • the insecticide is a Nicotinic acetylcholine receptor allosteric activator.
  • the Nicotinic acetylcholine receptor allosteric activator is a spinosyn, optionally Spinosad, spineto-ram, or a combination thereof.
  • the insecticide is a chloride channel activator.
  • the chloride channel activator is from the class of avermectins and milbemycins, optionally abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin, or a combination thereof.
  • the insecticide is a juvenile hormone mimic.
  • the juvenile hormone mimic is hydroprene, kino-prene, methoprene; fenoxycarb, pyriproxyfen, or a combination thereof.
  • the insecticide is a Miscellaneous multi-site inhibitor.
  • the Miscellaneous multi-site inhibitor is an alkyl halide including CHsBr, chloropicrin, sulfuryl fluoride, borax, tartar emetic, or a combination thereof.
  • the insecticide is a Chordotonal organ TRPV channel modulator.
  • the Chordotonal organ TRPV channel modulator is afidopyropen, pymetrozine, pyrifluquinazon, or a combination thereof.
  • the insecticide is a mite growth inhibitor.
  • the mite growth inhibitor is clofentezine, hexythiazox, diflovidazin, etoxazole, or a combination thereof.
  • the insecticide is a Microbial disruptors of insect midgut membrane.
  • the microbial disruptors of insect midgut membrane is Bacillus thuringiensis, Bacillus sphaericus, and/or the insecticidal proteins they produce, optionally Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Abl, or a combination thereof.
  • the insecticide is an inhibitor of mitochondrial ATP synthase.
  • the inhibitor of mitochondrial ATP synthase is diafenthiuron, organotin miticides, optionally azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon, or a combination thereof.
  • the insecticide is an uncouplers of oxidative phosphorylation via disruption of the proton gradient.
  • the uncouplers of oxidative phosphorylation via disruption of the proton gradient is chlorfenapyr, DNOC, sulfluramid, or a combination thereof.
  • the insecticide is a nAChR channel blocker.
  • the nAChR channel blocker is a nereistoxin analogues bensultap, cartap hydrochloride, thio-cyclam, thiosultap-sodium, or a combination thereof.
  • the insecticide is an inhibitor of the chitin biosynthesis type 0.
  • the inhibitor of the chitin biosynthesis type 0 is bistrifluron, chlorfluazuron, difluben-zuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, or a combination thereof.
  • the insecticide is an inhibitor of the chitin biosynthesis type 1, optionally buprofezin.
  • the insecticide is a molting disruptor.
  • the molting disruptor is Dipteran, cyromazine, or a combination thereof.
  • the insecticide is an Ecdyson receptor agonist.
  • the Ecdyson receptor agonist is methoxyfenozide, tebufenozide, halofenozide, fufeno-zide, chromafenozide, or a combination thereof.
  • the insecticide is a Octopamin receptor agonist, optionally amitraz.
  • the insecticide is a Mitochondrial complex III electron transport inhibitor.
  • the Mitochondrial complex III electron transport inhibitor is hydramethylnon, acequinocyl, fluacrypyrim, bifenazate, or a combination thereof.
  • the insecticide is a METI acaricides and insecticide.: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, rotenone, or a combination thereof.
  • the insecticide is a Voltage-dependent sodium channel blocker: indoxacarb, metaflumizone, 2-[2-(4-cy _, anophenyl)-l-[3- (trifluoromethyl)phenyl] _, ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydra _, zine- carboxamide, N-(3-chloro-2-methyHphenyl)-2-[(4-chlorophenyl)[4-[methyl(methyHsul- fonyl)ami _, no]phenyl] _, methylene]-hydrazinecarboxamide, N-[4-chloro-2-[[(l,l- dimethylethyl)ami _, no]carbo _, nyl]-6-methylphenyl]-l-(3-chloro-2-pyridinyl)-3
  • the insecticide is an inhibitor of acetyl CoA carboxylase.
  • the inhibitor of acetyl CoA carboxylase is spirodiclofen, spiromesifen, spirotetramat, spiropidion, spirobudifen, 1 l-(4-chloro-2,6-dimethylphenyl)-12- hydroxy-l,4-dioxa-9-azadispiro[4.2.4.2]tetradec-l l-en-10-one, spidoxamat, or a combination thereof.
  • the insecticide is a Mitochondrial complex IV electron transport inhibitor.
  • the Mitochondrial complex IV electron transport inhibitor is aluminum phosphide, calcium phosphide, zinc phosphide, cyanide, or a combination thereof.
  • the insecticide is a mitochondrial complex II electron transport inhibitor.
  • the mitochondrial complex II electron transport inhibitor is cyenopyrafen, cyflumetofen, cyetpyrafen, pyflubumide, or a combination thereof.
  • the insecticide is a ryanodine receptor-modulator.
  • the ryanodine receptor-modulator is chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, fluchlordiniliprole, (R)-3-chloro-Nl- ⁇ 2- methyl-4-[ 1 ,2,2,2-tetrafluoro- 1 -(trifluoro _, methyl)ethyl]phenyl ⁇ -N2-(l -methyl-2- methylsulfonylethyl)phthalamid, (S)-3 -chloro-N 1 - ⁇ 2-methyl-4-[ 1 ,2,2,2-tetrafluoro- 1 - (trifluoromethyl)ethyl]phenyl ⁇ -N2-(l-methyl-2-methyl _, sulfonylethyl)phthal _, amide, methyl- 2-[3,5-dibromo-2-( ⁇ [3-bromo-l-(3-ch
  • the insecticide is a Chordotonal organ Modulator, optionally flonicamid.
  • the insecticide is a GABA gated chlorine channel allosteric modulator.
  • the GABA gate chlorine channel allosteric modulator is broflanilide, fluxametamide, isocycloseram, or a combination thereof.
  • the insecticide is Calcium-activated potassium channel modulator, optionally acynonapyr.
  • the insecticide is a Mitochondrial complex III electron transport inhibitor QI site, optionally Flometoquin.
  • the insecticide is Chordotonal organ modulators-undefmed target site, optionally Dimpropyridaz.
  • the insecticide is afoxolaner, azadirachtin, amidoflumet, ben- zoximate, bromopropylate, chino _, methionat, cryolite, cyproflanilid, dicloromezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, mivorilaner, modoflaner, piperonyl butoxide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, 1 l-(4-chl oro-2, 6-dimethylphenyl)-12-hydroxy- l,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-l l-en-10-one, 3-(
  • the insecticide is acephate, fipronil, cypermethrin, bifenthrin, tefluthrin, cyhalothrin, clothianidin, dinotefuran, imidacloprid, thiacloprid, thiamethoxam, sulfoxalor, spinosad, spientoram, emamectin, abamectin, pymetrozine, flonicamid, chlorfenapyr, buprofezin, metaflumizone, cyflumetofen, chlorantraniliprole, tetraniliprole, cyantraniliprole, tiorantraniliprole, pioxaniliprole, fluchlordiniliprole, afidopyropen, dimpropyridaz, fenmezoditiaz, sulfiflumin, broflanil
  • the cyclodextrin is a molecular basket.
  • the cyclodextrin is conjugated to a nanoparticle by a linker.
  • the linker is 4-caryboxylphenyl boronic acid (CBPA).
  • the linker is 4-aminophenylboronic acid.
  • a composition can comprise an effective amount of a conjugate comprising a cyclodextrin conjugated to a nanoparticle, wherein the cyclodextrin comprises a pesticide, optionally an insecticide.
  • the composition further comprises diluents, preservatives, organic solvents, solubilizers, emulsifiers, surfactants, dispersants, preservatives, colorants, fillers, diluents, binders, glidants, lubricants, disintegrants, anti-adherents, sorbents, coatings, wetting agents, penetrants, vehicles, or a combination thereof.
  • the composition is formulated as a liquid, powder, suspension, paste, pellet, or gel.
  • the insecticide is present in an amount ranging from 0.001 to 10,000 ppm, 0.1 to 2000 ppm, or 1 to 1000 ppm.
  • a method of treating a plant can comprise contacting a plant with an effective amount of a conjugate or composition comprising a cyclodextrin conjugated to a nanoparticle, wherein the cyclodextrin comprises a pesticide, optionally an insecticide.
  • the plant is suffering from a pest infestation, optionally an insect infestation, a nematode infestation, an arachnid infestation, or a combination thereof.
  • a method of pest control of a plant can comprise contacting a plant with an effective amount of a conjugate or composition comprising a cyclodextrin conjugated to a nanoparticle, wherein the cyclodextrin comprises a pesticide, optionally an insecticide.
  • the pesticide is an insecticide.
  • the pest is an insect, an arachnid, a nematode, or a combination thereof.
  • the insect is from the order Lepidoptera.
  • the insect is Helicoverpa spp., Heliothis virescens, Lobesia botrana, Ostrinia nubilalis, Plutella xylostella, Pseudoplusia includens, Scirpophaga incertulas, Spodoptera spp., Trichoplusia ni, Tuta absoluta, Cnaphalocrocis medialis, Cydia pomonella, Chilo suppressalis, Anticar sia gemmatalis, Agrotis ipsilon, Chrysodeixis includens, or a combination thereof.
  • the insect is from the order Hemiptera.
  • the insect is selected from Lyguss spp.
  • the insect is a stink bug.
  • the insect is Euschistus spp., Halyomorpha halys, Nezara viridula, Piezodorus guildinii, Dichelops furcatus, or a combination thereof.
  • the insect is a thrip.
  • the insect is Frankliniella spp., Thrips spp., Dichromothrips corbettii, or a combination thereof.
  • the insect is an aphid.
  • the insect is Acyrthosiphon pisum, Aphis spp., Myzus persicae, Rhopalosiphum spp., Schizaphis graminum, Megoura viciae, or a combination thereof.
  • the insect is a whitefly.
  • the insect is Trialeurodes vaporariorum, Bemisia spp., or a combination thereof. [0099] In an embodiment, the insect is from the order Coleoptera.
  • the insect is Phyllotreta spp., Melanotus spp., Meligethes aeneus, Leptinotarsa decimlineata, Ceutorhynchus spp., Diabrotica spp., Anthonomus grandis, Atomaria linearia, Agriotes spp., Epilachna spp., or a combination thereof.
  • the insect is a fly.
  • the insect is Delia spp., Ceratitis capitate, Bactrocera spp., Liriomyza spp., or a combination thereof.
  • the insect is from the order Coccoidea.
  • the insect is Aonidiella aurantia, Ferrisia virgate, or a combination thereof.
  • the pest is from the order Arachnida.
  • the pest is Penthaleus major, Tetranychus spp., or a combination thereof.
  • the pest is a nematode.
  • the pest is Heterodera glycines, Meloidogyne sp., Pratylenchus spp., Caenorhabditis elegans, or a combination thereof.
  • the pest is a member of the Pentatomidae family.
  • the pest infestation is on a leaf, stem, root, or a combination thereof.
  • the pesticide optionally an insecticide enters through the insect tarsi, optionally tarsal pores.
  • the insecticide can enter through the insect tarsi, optionally tarsal pores.
  • the pesticide optionally an insecticide
  • the insecticide does not significantly penetrate the cuticle of the plant.
  • FIG. 1 depicts the targeted carbon dot based nanocarriers for the delivery of chemical cargoes to stink bugs (Nezara viridula).
  • Nanocarriers composed of carbon dots (CDs) with molecular baskets (y-cyclodextrins), were specifically designed with size and charge properties that facilitate their spontaneous translocation through the stink bug leg tarsal surface and effectively reduce the delivery of chemical cargoes through the plant leaf surface.
  • the inventors used Gds doping of CDs (GdCDs) to detect nanocarriers by elemental analysis in stinkbugs.
  • the fluorescence properties of the CDs and their chemical cargoes allows high resolution imaging by confocal microscopy. This nanotechnology-based approach offers the potential to enhance the delivery efficiency of insecticide active ingredients, while simultaneously reducing losses in the environment.
  • Figures 2A-2J depicts the characterization of nanocarriers made of carbon dots and molecular baskets and loading of fluorescent chemical cargo.
  • Figure 2A Schematic depicts the steps for y-cyclodextrin modifications of GdCDs (y-GdCDs) and CDs (y-CDs).
  • Figure 2B AFM image of GdCDs and
  • Figure 2C y-GdCDs with their height profile.
  • Figures 3A-3C depicts the nanocarrier and chemical cargo interactions with plant leaf surface.
  • Figures 3 A Confocal images of leaves after 3 h incubation with nanocarriers. Cyan indicates y-GdCDs fluorescence (Ex. k- 355 nm), yellow indicates R6G dye fluorescence (Ex. - 488 nm), and magenta indicates chloroplast autofluorescence. Green indicates the colocalization of y-GdCDs with R6G dye.
  • Figures 4A-4B depicts the optical and physical properties of stink bug tarsi.
  • FIG. 4B SEM images of N viridula tarsi, (i) Ventral view of three tarsal segments (Tl- T3) and pretarsus (PR), (ii) Ventral view of PR showing an unguitractor plate (U), basipulvillus (BP), two pulvilli (P), two curved claws (CL), and two parapodia (PA), (iii-vi) High magnification images of pulvilli (iii,iv) and T1 (v,vi). Black arrows indicate the pores present on the tarsal surface. Inset in (vi) shows the magnified image of glands highlighted in black circles.
  • Figures 5A-5B depict the fluorescent chemical cargo delivery to stink bugs tarsi by nanocarriers.
  • Figure 5 A Steps to determine the uptake of Nile red delivered by y-GdCDs nanocarriers to N. viridula tarsi via confocal microscopy.
  • Figures 6A-6D depict the efficacy of nano formulation on N. viridula mortality.
  • Figure 6A Cumulative mortality of Nezara viridula caused by Al delivered in y-CDs compared to Al alone, y-CDs alone, and 0.1% triton-x 100 alone.
  • Figure 6B Toxicity of Al delivered by y-CDs compared to Al alone and y-CDs alone on bugs after removing their stylets. Each treatment contained 10 bugs on 10 leaves in separate petri dishes and the treatments were replicated 3 times.
  • Asterisks in A and B indicate significant differences between insect mortality caused by y-CDs-AI and Al alone (Tukey's post hoc test, **P ⁇ 0.001 and ****P ⁇ 0.0001).
  • FIG. 6C Comparative analysis of stink bug mortality caused by y-CDs- Al on whole insects and insects after removal of their stylets.
  • Figure 7A depicts a schematic depicting the stepwise synthesis of y-cyclodextrin modified GdCDs (y-GdCDs), and Figure 7B depicts a schematic depicting the stepwise synthesis of CDs (y-CDs).
  • Figure 8A depicts the absorbance of CDs and y-CDs showed two absorbance peaks at 334 nm and 394 nm and Figure 8B depicts the fluorescence spectra of CDs and y-CDs showed fluorescence emission maxima at 450 nm.
  • Figure 9A depicts the absorbance spectra of Nile red dye in the presence of different percentages of dimethyl sulfoxide (DMSO) in deionized water.
  • Figure 9B depicts the solubility of dye in different percentages of DMSO in deionized water.
  • DMSO dimethyl sulfoxide
  • Figure 10A depicts the absorbance of y-GdCDs, R6G, and y-GdCDs-R6G.
  • the spectra of y-GdCDs-R6G shows that in addition to the y-GdCDs peak at 350 nm, a new peak at 525 nm appeared, which matches with the R6G absorbance peak (inset shows the clear R6G absorbance peak at 525 nm in y-GdCDs-R6G).
  • Figure 10B depicts the fluorescence spectra of y-GdCDs, R6G, and y-GdCDs-R6G.
  • Figure 13 depicts the FTIR spectrum of y-CDs alone, Al alone, and y-CDs-AI.
  • the FTIR spectrum of y-CDs-AI showed the appearance of several new peaks that match the peaks of bare Al, in addition to the peaks corresponding to y-CDs.
  • Figure 14 depicts photographs of experimental set-up showing four different treatment groups used in mortality experiments.
  • Figures 16A-16B depict photographs of stink bugs with and without stylet.
  • Figure 16A Photographs of stink bugs with stylet.
  • Figure 16B Photographs of stink bugs without stylet. Black arrow in (A) shows the presence of needle like stylet, whereas (B) shows the absence of the stylet.
  • Figure 17 depicts a digital photograph of a soybean leaf placed on a 1% agar plate reveals the presence of moisture on leaf surface, which can serve as a medium for the uptake of nanocarrier present on leaf surface by the stink bugs, potentially through their tarsi.
  • Pesticide refers broadly to a chemical agent used to kill or inhibit a pest and/or pathogen. Pests include, but are not limited to, arthropods, optionally, insects, arachnids, and their larvae and eggs. In an embodiment, the pest is a stink bug. Pathogens include, but are not limited to, fungi, viruses, and bacteria. A pest could be a transmission vector for a pathogen. Inhibition of a pest and/or a pathogen could promote the health and/or growth of a plant, and/or treat a disease of a plant infested or infected by a pest and/or a pathogen. An “insecticide” can be a natural or synthetic organic compound. The insecticide can be an anti-microbial agent, for example, a fungicide or bactericide (, optionally, antibiotic agent).
  • “Functionalized” or “functionalization,” as used herein, refers broadly to a compound or material (, optionally, a nanoparticle) that has been modified to confer additional function to the compound or material (, optionally, a function of targeting or a function of having enhanced cargo loading capacity).
  • a nanoparticle can be functionalized by linking a gamma-cyclodextrin and/or molecular basket to its surface.
  • “Linked,” as used herein, refers broadly to a linkage of two elements in a functional relationship.
  • “linked” can refer to a linkage of an insecticide and a targeting agent in a functional relationship.
  • linked also refers to the linkage/association of two chemical moieties so that the location or biodistribution of one might be affected by the other.
  • an insecticide is said to be “linked to” or “associated with” a targeting moiety, wherein after the introduction of an insecticide to a plant in need thereof, the cargo’s transport/biodistribution into and within the plant is affected by the linked targeting moiety.
  • the functional relationship between the cargo and the linked targeting moiety can involve co-transportation and/or colocalization within certain plant compartments (, optionally, leaf, stem, root, or vasculature, e.g., phloem).
  • “Introduce,” as used herein, refers broadly to contacting a plant, or a portion thereof, with a material (, optionally, a conjugate described herein).
  • a conjugate or a composition comprising the conjugate can be applied to the plant, or a portion thereof (, optionally, leaf or spore).
  • the plant, or a portion thereof (, optionally, foliage and/or other tissues), is sprayed with the conjugate or a composition comprising the conjugate.
  • the plant, or a portion thereof, is coated with the conjugate or a composition comprising the conjugate (, optionally, a leaf dipped in a composition).
  • the conjugate or a composition comprising the conjugate is administered to the plant (, optionally, via injection).
  • Effectivee amount refers broadly to an amount of a conjugate as described herein to inhibit a pest and/or pathogen.
  • Soybean (Glycine max L.) is an important crop affected by the southern green stink bug (Nezara viridula L), and accounting for 53% of the world’s oilseed crops. Giacometti, R. et al. Sci. Rep. 10, 15468 (2020); Pratap et al. Chapter 12 - Soybean, in Breeding Oilseed Crops for Sustainable Production (ed. Gupta, S. K.) 293-315 (Academic Press, 2016); Nair et al. Global Status of Vegetable Soybean. Plants 12, (2023). This stink bug causes damage to soybean foliage and beans by using their piercing-sucking stylets to inject digestive enzymes into the plant tissue and sucking their fluids.
  • Nanomaterials hold great promise in the development of new technologies and strategies for crop pest management. Their unique physicochemical properties have been explored for controlled and targeted delivery applications in plants, presenting a tremendous potential to improve the insecticide efficiency while reducing their environmental impact. NMs delivery efficiency can be adjusted by manipulating their size, charge, surface area, and polarity. NMs penetration through the insect cuticle. Insecticide active ingredient (Al) delivery is increased by nanocarriers to the stink bugs via tarsal pores as a route for the Al delivery in insects that would enhance mortality.
  • Al Insecticide active ingredient
  • CDs Carbon dots
  • CDs are preferred for delivery applications due to their unique properties of facile synthesis, small size, high aqueous solubility, internal fluorescence properties, biocompatibility, and degradability.
  • CDs have a beneficial effect on various plant physiological processes, including on growth, photosynthesis, and resistance to biotic/abiotic stress.
  • the surface functional groups present on CDs make them easily modifiable, enabling CDs as excellent nanocarriers for targeted delivery of chemical cargoes.
  • Cyclodextrins a class of non-toxic cyclic molecules made up of glucose units linked by a 1-4 glycosidic bonds, is a versatile tool for constructing smart nano-delivery systems in combination with other nanomaterials.
  • These molecular baskets with a hydrophobic internal cavity form an inclusion complex with hydrophobic compounds improving solubilization, slow release, reduced active ingredient (Al) evaporation, and stability in formulations of a wide range of chemicals. Therefore, by incorporating insecticide Al into cyclodextrin- modified CDs, the inventors surprisingly discovered that it improved their delivery and increase their efficacy against stink bugs.
  • Carbon dot nanocarriers with molecular baskets have been studied for chemical cargo delivery in plants but not in insect pests.
  • y-cyclodextrin-modified carbon dots act as a nanocarrier to deliver insecticide Al into the tarsi of stink bugs (N. viriduld), thereby increasing their efficacy and insect mortality.
  • the physicochemical properties of these nanocarriers after foliar application were designed to restrict their uptake through to the leaf surface, allowing the nanocarrier to contact and enter the bugs via the sub-micron sized pores present in their tarsi as they walk on the leaf surface ( Figure 1).
  • the fluorescence emitting properties of y-GdCD allowed tracking of their interactions in soybean leaves by confocal microscopy.
  • the uptake of nanocarriers to stink bugs through their tarsi and their ability to deliver the chemical cargoes was demonstrated with ICP-OES analysis of y-GdCD and confocal microscopy of y-GdCD loaded with Nile red dye, respectively.
  • an undoped y-CDs nanocarrier with comparable physiochemical properties to y-GdCD was synthesized and loaded with insecticide Al (y-CDs-AI) to demonstrate the efficacy of y-CDs-AI nano-formulation increasing stink bug mortality.
  • the inventors developed carbon dot-based nanocarriers (y-CDs-AI) for the enhanced delivery and efficacy of an insecticide to stink bug N. viridula through the tarsi.
  • the physicochemical properties of the nanocarrier maximizes the nano-formulation levels on the soybean leaf surface, allowing it to enter the stink bugs via sub-micron size pores in their tarsi as they walk on the leaf surface.
  • Elemental and confocal microscopy analysis indicated that y-GdCDs are uptaken through the insect tarsi and the delivery of Nile red is enhanced 2.6 times by the nanocarriers.
  • the y-CDs-AI increased the solubility of the hydrophobic active ingredient (Al) cargoes making it a more efficient formulation for crop protection against pests.
  • Nanocarrier mediated delivery of the active ingredient (Al) resulted in 25% higher mortality in stink bugs than the active ingredient (Al) alone.
  • Syletectomy studies indicated Al delivery through the tarsi by y-CDs-AI having -45% higher mortality compared to Al alone in insects with stylets removed.
  • the y-CDs-AI had a similar mortality regardless of stylet removal while Al alone showed 20% lower mortality in insects with their stylet removed.
  • Carbon dot based nanocarriers are a promising and sustainable approach for significantly enhancing the delivery and efficacy of insecticide active ingredient (Al) through a novel non- classical route.
  • the development of y-CDs-AI enabling a more precise delivery of Al on the leaf surface in direct contact with insect pests can lead to significant reductions in overall Al needed to manage N viridula and other insects that have
  • the disclosure provides a conjugate comprising a cyclodextrin linked to an insecticide.
  • the disclosure provides a conjugate comprising a cyclodextrin linked to an pesticide, optionally an insecticide.
  • the cyclodextrin can be gamma-cyclodextrin.
  • Nanocarriers composed of carbon dots (CDs) with molecular baskets (y-cyclodextrins), were specifically designed with size and charge properties that facilitate their spontaneous translocation through the insect leg tarsal surface and effectively reduce the delivery of the insecticide through the plant leaf surface.
  • a conjugate described herein can comprise a cyclodextrin linked to an insecticide.
  • the insecticide may be linked directly or indirectly.
  • a conjugate described herein can comprise a cyclodextrin linked to a pesticide, optionally an insecticide.
  • the pesticide, optionally an insecticide can be linked directly or indirectly.
  • a conjugate described herein can comprise a cyclodextrin linked to a nanoparticle, wherein the conjugate is capable of being delivered to a plant, and the nanoparticle is a quantum dot, carbon dot, carbon nanotube, silica nanoparticle, optionally a porous silica nanoparticle, lipid nanoparticle, liposome, metal or metal oxide nanoparticle, and micro nutrient-based nanoparticle, macro nutrient-based nanoparticle, or a combination thereof.
  • the conjugate described herein can comprise a cyclodextrin linked to an insecticide.
  • the nanoparticle can be a quantum dot, carbon dot, carbon nanotube, silica nanoparticle, optionally porous silica nanoparticle, lipid nanoparticle, liposome, metal or metal oxide nanoparticle, a micronutrient-based nanoparticle, macro nutrient-based nanoparticle, or a combination thereof.
  • the nanoparticle can be a carbon dot (CD).
  • the nanoparticle can be a quantum dot, carbon dot, carbon nanotube, optionally a single walled carbon nanotube (SWCNT), silica nanoparticle, lipid nanoparticle, liposome, metal nanoparticle, metal oxide nanoparticle, and a micro nutrient-based nanoparticle, macro nutrient-based nanoparticle, or a mixture thereof.
  • SWCNT single walled carbon nanotube
  • the carbon nanotube can be a single walled carbon nanotube (SWCNT).
  • the silica nanoparticle can be a porous silica nanoparticle.
  • the silica nanoparticle can be a mesoporous silica nanoparticle.
  • the nanoparticle is a metal or metal oxide nanoparticle (optionally, gold, silver, copper, zinc, zinc oxide, magnesium, magnesium oxide, cerium oxide, or iron oxide nanoparticle).
  • the nanoparticle is not a metal or metal oxide nanoparticle (optionally, gold, silver, or iron oxide nanoparticle).
  • the nanoparticle can be a carbon dot comprising metal (optionally, metal doped carbon dot).
  • the nanoparticle can be a carbon dot that does not comprise metal.
  • the metal nanoparticle can be a gold, silver, copper, zinc, magnesium nanoparticle, or a mixture thereof.
  • the metal oxide nanoparticle can be a copper oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide nanoparticle, or a mixture thereof.
  • the micro nutrient-based nanoparticle can comprise nitrogen, phosphorus, copper, zinc, magnesium, or a mixture thereof.
  • the macro nutrient-based nanoparticle can comprise nitrogen, phosphorous, copper, zinc, magnesium, or a mixture thereof.
  • the nanoparticle can be between about 1 nm to 100 nm in size, optionally have a size distribution of between about 1 nm to 10 nm in size.
  • the nanoparticle can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm in size.
  • the nanoparticle can have a size of between about 1-9 nm, 2-8 nm, 2-7 nm, 3-6 nm, 4-5 nm, 1-4 nm, 2-3 nm, 1-2.5 nm, 4-8 nm, or 3-7 nm.
  • the nanoparticle can have an average size distribution of between about 1 nm and 10 nm.
  • the nanoparticle can have an average size distribution of between about 1 and 8 nm, 2 and 9 nm, 5 and 7 nm, 4 and 8 nm, or 3 and 9 nm.
  • the nanoparticle can have an average size distribution of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm.
  • the nanoparticle can have an average size of between about 1 and 100 nm, for example, the nanoparticle can have an average size of between about 1 nm and 50 nm, 20 nm and 80 nm, 40 nm and 60 nm, or 75 nm and 95 nm.
  • the nanoparticle can have an average size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 nm.
  • the nanoparticle can be between about 1 and 100 nm in size, for example, the nanoparticle can have a size of between about 1 nm and 50 nm, 20 nm and 80 nm, 40 nm and 60 nm, or 75 nm and 95 nm in size.
  • the nanoparticle can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,
  • the nanoparticle can be spherical or non- spherical.
  • Methods for characterizing nanoparticles or nanomaterials are known in the art and are described herein (optionally, electron microscopy, dynamic light scattering, transmission electron microscopy (TEM), or atomic force microscopy).
  • the nanoparticles can have spherical shapes with a size distribution in a range of about 4-8 nm.
  • the nanoparticle surface (optionally, a carbon dot, see Figure 1) can be dualfunctionalized with a cyclodextrin molecular basket, wherein insecticide loaded in the cyclodextrin molecular basket.
  • the nanoparticle can be a micro or macro nutrient-based nanoparticle that could serve as a nano-fertilizer that supplements a plant with micro or macro nutrient(s) (optionally, nitrogen, phosphorus, copper, zinc, or magnesium).
  • the nanoparticle can be a phosphorus nano-fertilizer, e.g., nano-sized hydroxyapatite (Cas(PO4)3OH).
  • the nanoparticle can be a urea-modified hydroxyapatite nanoparticle.
  • hydroxyapatite, metal, or metal oxide nanoparticles are known in the art and described herein.
  • the surface of a hydroxyapatite, metal or metal oxide nanoparticle can have a layer of silica coating (SiCh).
  • the surface of a hydroxyapatite, metal or metal oxide nanoparticle can be functionalized with a linker described herein including a silane-based molecule or a polymer, e.g., PEG that could be further functionalized with a gamma-cyclodextrin as described herein.
  • the nanoparticle can have a zeta potential magnitude of about 10 mV to 60 mV.
  • the insecticide can be a small molecule compound having a molecular weight of less than 1000 g/mol.
  • the insecticide can be a small molecule having a molecular weight of less than 800 g/mol.
  • the insecticide can be a small molecule having a molecular weight of less than 700 g/mol.
  • the insecticide can be a polypeptide or polynucleotide that kills or inhibits a pest.
  • the conjugate can optionally comprise a pesticide.
  • Embodiments of the disclosure can include one or more insecticides, including one or more of the following insecticides.
  • the following insecticides are grouped according to the Mode of Action Classification of the Insecticide Resistance Action Committee (IRAC):
  • AChE inhibitors aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifosmethyl, coumaphos, cyanophos, demeton-S-methyl, di
  • GABA-gated chloride channel antagonists cyclodiene organochlorine compounds: endosulfan, chlordane; phenylpyrazoles: ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole, or a combination thereof.
  • Sodium channel modulators pyrethroids, optionally acrinathrin, allethrin, d-cis- trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S- cylclopentenyl, bio-resmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta- cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etof
  • nAChR agonists neonicotinoids: acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; 4,5-dihydro-N-nitro-l-(2- oxiranylmethyl)-lH-imidazol-2-amine, (2E-)-l-[(6-Chloropyridin-3-yl)methyl]-N'-nitro-2- pentylidenehydrazinecarboximidamide; l-[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 5-propoxy-l,2,3,5,6,7-hexahydroimidazo[l,2-a]pyridine; nicotine; sulfoxaflor; flupyradifurone; triflumezopyrim, fenmezoditiaz, flupyrimin, or
  • Nicotinic acetylcholine receptor allosteric activators spinosyns, optionally spinosad or spinetoram.
  • Chloride channel activators from the class of avermectins and milbemycins optionally abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin, or a combination thereof.
  • Juvenile hormone mimics for example, hydroprene, kino-prene, methoprene; fenoxycarb, pyriproxyfen, or a combination thereof.
  • Miscellaneous multi-site inhibitors an alkyl halide including CHsBr, chloropicrin, sulfuryl fluoride, borax, tartar emetic, or a combination thereof.
  • Chordotonal organ TRPV channel modulators afidopyropen, pymetrozine, pyrifluquinazon, or a combination thereof.
  • Mite growth inhibitors clofentezine, hexythiazox, diflovidazin, etoxazole, or a combination thereof.
  • Microbial disruptors of insect midgut membranes Bacillus thuringiensis, Bacillus sphaericus, and/or the insecticidal proteins they produce, optionally Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Abl, or a combination thereof
  • Inhibitors of mitochondrial ATP synthase diafenthiuron, organotin miticides, optionally azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon, or a combination thereof.
  • nAChR channel blockers nereistoxin analogues bensultap, cartap hydrochloride, thio-cyclam, thiosultap-sodium, or a combination thereof.
  • Inhibitors of the chitin biosynthesis type 0 bistrifluron, chlorfluazuron, difluben- •on, fluey cl oxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, or a combination thereof.
  • Inhibitors of the chitin biosynthesis type 1 buprofezin.
  • Molting disruptors Dipteran, cyromazine, or a combination thereof.
  • Ecdyson receptor agonists methoxyfenozide, tebufenozide, halofenozide, fufeno- zide, chromafenozide, or a combination thereof.
  • Octopamin receptor agonists amitraz.
  • Mitochondrial complex III electron transport inhibitors hydramethylnon, acequinocyl, fluacrypyrim; bifenazate, or a combination thereof.
  • METI acaricides and insecticides fenazaquin, fenpyroximate, pyrimidifen, pyrida-ben, tebufenpyrad, tolfenpyrad, rotenone, or a combination thereof.
  • Inhibitors of the of acetyl CoA carboxylase spirodiclofen, spiromesifen, spirotetramat; spiropidion; spirobudifen, 1 l-(4-chl oro-2, 6-dimethylphenyl)-12-hydroxy- 1,4- dioxa-9-azadispiro[4.2.4.2]tetradec-l l-en-10-one, spidoxamat, or a combination thereof.
  • Mitochondrial complex IV electron transport inhibitors aluminium phosphide, calcium phosphide, zinc phosphide, cyanide, or a combination thereof.
  • Mitochondrial complex II electron transport inhibitors cyenopyrafen, cyflumetofen, cyetpyrafen, pyflubumide, or a combination thereof.
  • Ryanodine receptor-modulators chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, fluchlordiniliprole, (R)-3-chloro-Nl- ⁇ 2-methyl-4-[l, 2,2,2- tetrafluoro- 1 -(trifluoromethyl)ethyl]phenyl ⁇ -N2-( 1 -methyl-2- methylsulfonylethyl)phthalamid, (S)-3 -chloro-N 1 - ⁇ 2-methyl-4-[ 1 ,2,2,2-tetrafluoro- 1 - (trifluoromethyl)ethyl]phenyl ⁇ -N2-(l-methyl-2-methylsulfonylethyl)phthalamide, methyl-2- [3,5-dibromo-2-( ⁇ [3-bromo-l-(3-chlorpyridin-2-yl)-lH-pyrazol-5-yl
  • GABA gated chlorine channel allosteric modulators broflanilide; fluxametamide, isocycloseram, or a combination thereof.
  • Calcium-activated potassium channel modulators acynonapyr.
  • Mitochondrial complex III electron transport inhibitor QI site Flometoquin.
  • Chordotonal organ modulators-undefined target site Dimpropyridaz.
  • insecticides include: afoxolaner, azadirachtin, amidoflumet, ben- zoximate, bromopropylate, chino _, methionat, cryolite, cyproflanilid, dicloromezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, mivorilaner, modoflaner, piperonyl butoxide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, 1 l-(4-chl oro-2, 6-dimethylphenyl)-12-hydroxy- l,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-l l-en-10-one, 3-(4-chl oro
  • the insecticides can further comprise biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, ( ,Z)-7,9- dodecadien-l-yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)- 7,11,13 -hexadecatri enal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cisjasmone, 2-methyl 1-butanol, methyl eugenol, methyl jasmonate, (E,Z)-2, 13 -octadecadi en-1- ol, (/'/Z)-2, l 3 -octadecadi en
  • Any one or a combination of any of the insecticides can be selected.
  • the insecticide can be selected from the group consisting of acephate, cypermethrin, cyhalothrin, bifenthrin, imidacloprid, acetamiprid, dinotefuran, thiacloprid, chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, broflanilide, isocycloseram, or combinations thereof.
  • the insecticide can be present in compositions in a range from 0.001 to 10,000 ppm, preferably from 0.1 to 2000 ppm, most preferably from 1 to 1000 ppm.
  • the insecticide can comprise a combination of any of the insecticides listed herein, for example, the insecticide can comprise a combination of a AChE inhibitor, GABA-gated chloride channel antagonist, Sodium channel modulator, nAChR agonist, nicotinic acetylcholine receptor allosteric activator, chloride channel activator, juvenile hormone mimic, chordontonal organ TRPV channel modulator, mite growth inhibitor, inhibitor of mitochondrial ATP synthase, uncoupler of oxidative phosphorylation, inhibitor of the chitin biosynthesis type 0, ecdyson receptor agonist, METI acaricide and insecticide, voltagedependent sodium channel blocker, inhibitor of the acetyl CoA carboxylase, mitochondrial complex II electron transport inhibitor, ryanodine receptor-modulator, chordontonal organ modulator, GABA gated chlorine channel allosteric modulator, calcium-activated potassium channel modulator, mitochondrial complex III electron transport inhibitor QI site, chordontonal organ modulators-un
  • the insecticide can be acephate, cypermethrin, cyhalothrin, bifenthrin, imidacloprid, acetamiprid, dinotefuran, thiacloprid, chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, broflanilide, isocycloseram, or a combination thereof.
  • the insecticide can be associated with a cyclodextrin molecular basket.
  • the insecticide can be loaded within a cyclodextrin molecular basket.
  • the insecticide forms an inclusion complex with the cyclodextrin. Therefore, the insecticide can be indirectly linked to the gamma-cyclodextrin via the cyclodextrin molecular basket (optionally, that is functionalized with the gamma-cyclodextrin; or that is linked to a nanoparticle functionalized with the gamma-cyclodextrin).
  • the loading of the insecticide in the cyclodextrin molecular basket allows for a controlled release of the insecticide.
  • the pesticide can be associated with a cyclodextrin molecular basket.
  • the insecticide can be loaded within a cyclodextrin molecular basket.
  • the insecticide forms an inclusion complex with the cyclodextrin. Therefore, the pesticide, optionally an insecticide, can be indirectly linked to the gamma-cyclodextrin via the cyclodextrin molecular basket (optionally, that is functionalized with the gamma-cyclodextrin; or that is linked to a nanoparticle functionalized with the gamma-cyclodextrin).
  • the loading of the pesticide, optionally an insecticide, in the cyclodextrin molecular basket allows for a controlled release of the pesticide, optionally an insecticide.
  • the cyclodextrin forming the molecular basket can comprise an alpha-cyclodextrin, beta- cyclodextrin, gamma-cyclodextrin, or a combination thereof.
  • the cyclodextrin can be a gamma-cyclodextrin.
  • the insecticide can form a complex with the molecular basket (optionally, loaded into a molecular basket).
  • the cyclodextrin molecular basket can be linked either directly or indirectly to a nanoparticle.
  • a conjugate comprising a gamma-cyclodextrin linked to a cargo, wherein the conjugate is capable of being delivered to a plant (, optionally, to a desired site within the plant, e.g., a leaf), and wherein the cargo is an agent that is capable of producing a desired effect in the plant following delivery of the conjugate to the plant.
  • a conjugate comprising a gamma-cyclodextrin or a gamma-cyclodextrin linked to a cargo that is an insecticide.
  • a conjugate as described herein comprises a mixture of cyclodextrins.
  • a conjugate comprising a gamma-cyclodextrin or a gamma-cyclodextrin linked to a cargo that is a pesticide, optionally an insecticide.
  • a conjugate as described herein comprises a mixture of cyclodextrins.
  • the conjugate can comprise a nanoparticle and a cyclodextrin molecular basket.
  • a nanoparticle (NP) and a cyclodextrin molecular basket conjugate can serve as delivery vehicle for an insecticide.
  • insecticide can be carried within the cyclodextrin molecular basket and can be released on the surface of a plant.
  • a gamma-cyclodextrin a higher proportion of the conjugate described herein can be introduced to a plant surface and reach a target site of action (, optionally, leaf surface), improving available insecticide.
  • a higher proportion of the conjugate can be applied to a plant as compared to a control delivery vehicle without the gamma-cyclodextrin.
  • the conjugate can have an average size of between about 1 nm and 10 nm.
  • the conjugate can have an average size of between about 3 and 6 nm, 4 and 8 nm, 5 and 9 nm.
  • the conjugate can have an average size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm.
  • the conjugate diameter is a hydrodynamic diameter (, optionally, determined by dynamic light scattering).
  • the conjugate diameter is determined by electron microscopy.
  • the nanoparticle or a conjugate diameter can be determined by atomic force microscopy (AFM) or transmission electron microscopy (TEM).
  • a composition can comprise a conjugate described herein.
  • a conjugate as described herein can be formulated into a suitable dosage form for plant application/introduction.
  • Common agrochemical formulations include but are not limited to liquid and solid formulations.
  • Exemplary formulations include gel, aqueous or oil-based solutions, dispersions, suspensions or emulsions.
  • the conjugate can be formulated in a liquid formulation, which can be administered or sprayed onto a plant using, optionally, ground/aerial spraying.
  • the conjugate can be formulated in pellet or tablet formulations. Such formulations can be capable of rapid break-up in water using minimal or no agitation while providing fine dispersions of the active ingredient.
  • the composition can comprise agriculturally acceptable additives or excipients.
  • Suitable additives or excipients include but are not limited to organic solvents, solubilizers, emulsifiers, surfactants, dispersants, preservatives, colorants, fillers, diluents, binders, glidants, lubricants, disintegrants, anti-adherents, sorbents, coatings, wetting agents, penetrants, vehicles, and combinations thereof.
  • additives or excipients include but are not limited to organic solvents, solubilizers, emulsifiers, surfactants, dispersants, preservatives, colorants, fillers, diluents, binders, glidants, lubricants, disintegrants, anti-adherents, sorbents, coatings, wetting agents, penetrants, vehicles, and combinations thereof.
  • additives or excipients include but are not limited to organic solvents, solubilizer
  • a composition described herein can comprise a surfactant.
  • the surfactant can be a non-ionic surfactant (optionally, organosilicone surfactant Silwet, e.g., Silwet L-77).
  • the surfactant can improve the spreading of the composition (optionally, liquid composition) on the leaf surface, and/or can facilitate the uptake of a conjugate described herein across the leaf lamina.
  • the surfactant can facilitate uptake into leaf stomatai pores and/or increase permeability in the leaf epidermal layer, optionally, through partial removal of the cuticular layer.
  • the composition can be in a powder dosage form.
  • composition described herein can be in a lyophilized form and reconstituted into liquid form before use.
  • a linker can link a nanoparticle to a cyclodextrin molecular basket.
  • the linker can be 4-caryboxylphenyl boronic acid (CBPA).
  • the linker can be 4-aminophenylboronic acid.
  • a method of treating a plant (optionally, comprising a pest) in need thereof can comprise contacting the plant with an effective amount of a conjugate as described herein.
  • a method of treating a plant in need thereof, wherein the plant has a phloem pathogen or a root pathogen the method comprising contacting the plant with an effective amount of a conjugate as described herein.
  • Contacting the plant can comprise contacting a leaf of the plant. Contacting the plant can comprise contacting the top surface of a leaf of the plant.
  • the delivered conjugate is more efficiently delivered into the stem and/or root of the plant as compared to a control material that is not linked with the gamma-cyclodextrin.
  • the plant can be a fruit, vegetable, field crop, or a combination thereof.
  • the field crop can be what, oat, com soybean, rice, barley, or a combination thereof.
  • the vegetable crop can be lettuce, broccoli, carrot, spinach, pepper, or a combination thereof.
  • the fruit crop can be apple, orange, pear, grape, peach, or combination thereof.
  • the plant can be a nut tree, optionally an almond, walnut, pecan tree, or combination thereof.
  • the plant can be cotton, flax, or a combination thereof.
  • the plant can be blackberry, cabbage, com, tomato, eggplant, bean, soybean, or a combination thereof.
  • the plant can be a tree, optionally apple, peach, pecan, cherry, or a combination thereof.
  • the plant can be a columbine, snapdragon, sunflower, or a combination thereof.
  • the compounds of the disclosure are especially suitable for efficiently combating animal pests, optionally arthropods, gastropods, nematodes, or combinations thereof, including, but not limited to:
  • Insects from the order of Lepidoptera optionally Achroia grisella, Acleris spp., optionally A. fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp., optionally A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp., optionally A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A.
  • Argyresthia conjugella Argyroploce spp., Argyrotaenia spp., optionally A. velutinana
  • Athetis mindara Austroasca verdigrises, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busse ola spp., Cacoecia spp., optionally C. murinana, C.
  • Cactoblastis cactorum Cadra cautella, Calingo braziliensis, Caloptilis theivora, Capua reticulana, Carposina spp., optionally C. niponensis, C. sasakii; C ephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp., optionally C. Indicus, C. suppressalis, C. partellus; Choreutis pariana, Choristoneura spp., optionally C. conflictana, C. fumiferana, C. longicellana, C. murinana, C. occidentalis, C.
  • pomonella C. latiferreana; Dalaca noctuides, Datana integerrima, Dasychira pinicola, Dendrolimus spp., optionally D. pini, D. spectabilis, D. sibir icus; Desmia funeralis, Diaphania spp., optionally D. nitidalis, D. hyalinata; Diatraea grandiosella, Diatraea saccharalis, Diphthera f estiva, Earias spp., optionally E. insulana, E.
  • kuehniella kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp., optionally F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp., optionally G. funebrana, G. molesta, G.
  • Mamestra spp. optionally M. brassicae, M. configurata; Mamstra brassicae, Manduca spp., optionally M. quinquemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mods spp., optionally M. lapites, M.
  • operculella Phyllocnistis citrella, Phyllonorycter spp., optionally P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp., optionally P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathypena scabra, Platynota spp., optionally P. flavedana, P. idaeusalis, P.
  • Virachola spp. Yponomeuta padella, and Zeiraphera canadensis.
  • Insects from the order of Coleoptera optionally Acalymma vittatum, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus spp., optionally A. anxius, A. planipennis, A. sinuatus; Agriotes spp., optionally A. fuscicollis, A. lineatus, A.
  • Attagenus spp. Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp., optionally B. lentis, B. pisorum, B. rufimanus; Byctiscus betulae, Callidiellum rufipenne, Callopistria jloridensis, Callosobruchus chinensis, Cameraria ohridella, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp., optionally C. assimilis, C.
  • Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp., optionally E. varivestis, E. vigintioctomaculata; Epitrix spp., optionally E. hirtipennis, E.
  • Eutheola humilis Eutinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hyper a spp., optionally H. brunneipennis, H.
  • hypomeces squamosus Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lerna spp., optionally L. bilineata, L. melanopus; Leptinotarsa spp., optionally L. decemlineata; Leptispa pygmaea, Limonius calif ornicus, Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp., optionally L.
  • Psacothea hilar is, Psylliodes chrysocephala, Prostephanus truncates, Psylliodes spp., Ptinus spp., Pulga saltona, Rhizopertha dominica, Rhynchophorus spp., optionally R. billineatus, R. ferrugineus, R. palmarum, R. phoenicis, R.
  • vulneratus vulneratus; Saperda Candida, Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp., optionally S. granaria, S. oryzae, S. zeamais; Sphenophorus spp., optionally S. levis; Stegobium paniceum, Sterne chus spp., optionally S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp., optionally T.
  • Insects from the order of Diptera optionally Aedes spp., optionally A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp., optionally A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A.
  • quinquefasciatus C. tarsalis, C. tritaeniorhynchus; Culicoides furens, Culiseta inornata, Culiseta melanura, Cuter ebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Dasineura oxycoccana, Delia spp., optionally D. antique, D. coarctata, D. platura, D. radicum; Dermatobia hominis, Drosophila spp., optionally D. suzukii, Fannia spp., optionally F. canicularis; Gastraphilus spp., optionally G.
  • Hypoderma spp. optionally H. lineata; Hyppobosca spp., Hydrellia philippina, Leptoconops torr ens, Liriomyza spp., optionally L. sativae, L. trifolii; Lucilia spp., optionally L. caprina,
  • Musca spp. optionally M. autumnalis, M. domestica; Muscina stabulans, Oestrus spp., optionally O. ovis; Opomyza florum, Oscinella spp., optionally O.frit;
  • Orseolia oryzae Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp., optionally P. antiqua, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis spp., optionally R. cerasi, R. cingulate, R. indiffer ens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp., optionally S.
  • Heliothrips spp. Hercinothrips femoralis, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kelly anus, Rhipiphorothrips cruentatus, Scirtothrips spp., optionally S. citri, S. dorsalis, S. perseae; Stenchaetothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp., optionally T. imagines, T. hawaiiensis, T. oryzae, T. palmi, T. parvispinus, T. tabaci.
  • Brachycaudus spp. optionally B. cardui, B. helichrysi, B. persicae, B. prunicola; Brachycolus spp., Brachycorynella as-paragi, Brevicoryne brassicae, Cacopsylla spp., optionally C. fulguralis, C.
  • Diaspis spp. optionally D. bromeliae; Dichelops furcatus, Diconocoris hewetti, Doralis spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp., optionally D. plantaginea, D. pyri, D. radicola;
  • Dysaulacorthum pseudosolani Dysdercus spp., optionally D. cingulatus, D. intermedins; Dysmicoccus spp., Edessa spp., Geocoris spp., Empoasca spp., optionally E.fabae, E. solana; Epidiaspis leper ii, Er iosoma spp., optionally E. lanigerum, E. pyricola;
  • Erythroneura spp., Eurygaster spp., optionally E. integriceps; Euscelis bilobatus, Euschistus spp., optionally E. her os, E. impictiventris, E. servus; Fiorinia theae, Geococcus cofifeae, Glycaspis brimblecombei, Halyomorpha spp., optionally H. halys; Heliopeltis spp., Homalodisca vitripennis ( H. coagulata), Horcias nobilellus, Hyalopterus pruni, Hyper omy zus lactucae, Icerya spp., optionally I.
  • Idiocerus spp. Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp., optionally L. ulmi; Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp., optionally L. hesperus, L. lineolaris, L. praten-sis; Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus, Macrosiphum spp., optionally M. rosae, M.
  • Psy Ila spp. optionally P. mali
  • Pteromalus spp. Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., optionally Q. perniciosus
  • Quesada gigas Rastrococcus spp., Reduvius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp., optionally R. pseudobrassicas, R. inser turn, R. maidis, R.
  • T. perditor Tibraca spp., Tomaspis spp., Toxoptera spp., optionally T. aurantii; Trialeur odes spp., optionally T. abutilonea, T. ricini, T. vapor ariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp., optionally U ci tri, U yanonensis; and Viteus vitifolii.
  • Insects from the order Hymenoptera optionally Acanthomyops interjectus, Athalia rosae, Atta spp., optionally A. capiguara, A. cephalotes, A. cephalotes, A. laevigata, A. robusta, A. sexdens, A. texana, Bombus spp., Brachymyrmex spp., Camponotus spp., optionally C. floridanus, C. pennsylvanicus, C.
  • geminata S.invicta, S. molesta, S. richteri, S. xyloni, Sphecius speciosus, Sphex spp., Tapinoma spp., optionally T. melanocephalum, T. sessile; Tetramorium spp., optionally T. caespitum, T. bicarinatum, Vespa spp., optionally V. crabro; Vespula spp., optionally V. squamosal; Wasmannia auropunctata, Xylocopa sp.
  • Pests from the Class Arachnida optionally Acari, optionally of the families Argasidae, Ixodidae and Sar-coptidae, optionally Amblyomma spp. (optionally A. americanum, A. variegatum, A. maculatum), Ar gas spp., optionally A. per sicu), Boophilus spp., optionally B. annulatus, B. decoloratus, B. microplus, Dermacentor spp., optionally D.silvarum, D. andersoni, D. variabilis, Hyalomma spp., optionally H. truncatum, Ixodes spp., optionally I.
  • ricinus, I. rubicundus, I. scapular is, I. holocyclus, I. pacificus, Rhipicephalus sanguineus, Ornithodorus spp., optionally O. moubata, O. hermsi, O. turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp., optionally P. ovis, Rhipicephalus spp., optionally R. sanguineus, R. appendiculatus, Rhipicephalus evertsi, Rhizogly phus spp., Sarcoptes spp., optionally S.
  • Tetranychidae including Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Petrobia latens, Tetranychus spp., optionally T. cinnabarinus, T. evansi, T. kanzawai, T, pacificus, T. phaseulus, T. telarius and T. urticae; Bryobia praetiosa; Panonychus spp., optionally P. ulmi, P. citri; Metatetranychus spp. and Oligonychus spp., optionally O. pratensis, O.
  • Pests from the Phylum Nematoda optionally plant parasitic nematodes, optionally root-knot nematodes, Meloidogyne spp., optionally M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp., optionally G. rostochiensis; Heterodera spp., optionally H. avenae, H. glycines, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp.; Stem and foliar nematodes, Aphelenchoides spp., optionally A.
  • Awl nematodes Dolichodorus spp.
  • Spiral nematodes Heliocotylenchus multicinctus
  • Sheath and sheathoid nematodes Hemicycliophora spp. and Hemicriconemoides spp.
  • Hirshmanniella spp. Lance nematodes, Hoploaimus spp.
  • False rootknot nematodes Nacobbus spp.
  • Needle nematodes Longidorus spp., optionally L. elongatus
  • Lesion nematodes Pratylenchus spp., optionally P.
  • brachyurus P. neglectus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nema-todes, Radopholus spp., optionally R. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylenchus spp., optionally R. robustus, R. reniformis: Sculellonema spp. Stubby-root nematode, Trichodorus spp., optionally T. obtusus, T. primitivus; Paratrichodorus spp., optionally P.
  • Stunt nematodes Tylenchorhynchus spp., optionally T. claytoni, T. dubius; Citrus nematodes, Tylenchulus spp., optionally T. semipenetrans; Dagger nematodes, Xiphinema spp., ' and other plant parasitic nematode species.
  • Pests from the class Chilopoda optionally Geophilus spp., Scutigera spp., optionally Scutigera coleoptrata.
  • Pests from the class Diplopoda optionally Blaniulus guttulatus, Julus spp., Narceus spp.
  • Pests from the class Symphyla optionally Scutigerella immaculata.
  • pests include, but are not limited to, Lepidoptera, optionally Helicoverpa spp., Heliothis virescens, Lobesia botrana, Ostrinia nubilalis, Plutella xylo Stella, Pseudoplusia includens, Scirpophaga incertulas, Spodoptera spp., Trichoplusia ni, Tuta absoluta, Cnaphalocrocis medialis, Cydia pomonella, Chilo suppressalis, Anticar sia gemmatalis, Agrotis ipsilon, Chrysodeixis includens; True bugs, optionally Lygus spp., Stink bugs, for example Euschistus spp., Halyomorpha halys, Nezara viridula, Piezodorus guildinii, Dichelops furcatus; Thrips, optionally Frankliniella spp., Thrips
  • Coleoptera optionally Phyllotreta spp., Melanotus spp.,Meligethes aeneus, Leptinotarsa decimlineata, Ceutorhynchus spp., Diabrotica spp., Anthonomus grandis, Atomaria linearia, Agriotes spp., Epilachna spp.;
  • Flies optionally Delia spp., Ceratitis capitate, Bactrocera spp., Liriomyza spp .; Coccoidea, optionally Aonidiella aurantia, Ferrisia virgate; Anthropods of class Arachnida (Mites), optionally Penthaleus major, Tetranychus spp. ; Nematodes, optionally Heterodera glycines, Meloidogyne sp., Pratylenchus spp., and Caenorhabditis elegans.
  • conjugates described herein and compositions comprising the conjugates described herein can be used in insect control for a plant.
  • conjugates described herein and compositions comprising the conjugates described herein can be used in pest control, optionally insect control, for a plant.
  • the plant can be achoccha, amaranth, angelica, anise, apple, arrowroot, arugula, artichoke, globe, artichoke, Jerusalem, asparagus, atemoya, avocado, balsam apple, balsam pear, bambara groundnut, bamboo, banana, plantains, barbados cherry, beans, beet, blackberry, blueberry, bok choy, boniato, broccoli, Chinese broccoli, raab broccoli, Brussels sprouts, bunch grape, burdock, cabbage, cabbage, sea-kale, swamp cabbage, calabaza, cantaloupes, muskmelons, capers, carambola (star fruit), cardoon, carrot, cassava, cauliflower, celeriac, celery, celtuce, chard, chaya, chayote, chicory, Chinese jujube, chives, chrysanthemum, chufa, cilantro, citron, coconut palm, collards
  • a method of treating an insect infestation in a plant can comprise contacting the plant with a conjugate described herein.
  • the plant can be sprayed, dipped, misted, or a combination thereof for application of the conjugate described herein.
  • GdCDs Gd 3+ doped carbon dots
  • reaction mixture was transferred to a 10 mL Teflon-lined stainless steel hydrothermal autoclave and heated at 180°C in a mechanical oven for 2 hours. After cooling down, the resulting dark brown dispersion was sonicated for 15 min at 80 kHz and centrifuged to remove large particles. The collected supernatant was filtered through 0.02 pm syringe filters (Anotop, Whatman, Germany) to further remove the large particles. Finally, the GdCDs dispersion was transferred to the dialysis membrane (MWCO: 1 kDa, Spectrum Labs) and dialyzed in molecular grade water for 48 h with regular water changes.
  • MWCO 1 kDa, Spectrum Labs
  • CDs undoped carbon dots
  • the CDs were synthesized by modifying a previously reported protocol. Khan et al. Sci. Rep. 7: 14866 (2017).
  • 2.40 g (40 mM) of urea (99.2%, Fisher) and 1.92 g (10 mM) of citric acid (Fisher, 99.7 %) were dissolved in 2 mL of molecular grade water in an agate mortar.
  • 1.35 mL of ammonium hydroxide (Sigma-Aldrich, 30-33%) solution was added.
  • the resulting reaction mixture was then heated in an oven at 180°C for 1.5 h.
  • the product was dissolved in 25 mL of molecular grade water and bath sonicated for 1 hour. The obtained dispersion was centrifuged at 4500 rpm for 30 min to remove the large aggregates. Finally, the CDs dispersion was transferred to the dialysis membrane (MWCO: 1 kDa) and dialyzed in molecular grade water for 48 hours with regular water changes.
  • MWCO dialysis membrane
  • EDC-HC1 l-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride
  • NHS N- hydroxysulfosuccinimide
  • CPBA 4-carboxyphenylboronic acid
  • the pH of the resulting CPBA-modified GdCDs and CDs dispersion was adjusted to 10.5 with NaOH (Sigma-Aldrich, 97%) in 10 mM TES buffer and 15 pL (62.5 mM) of y-cyclodextrin (TCI chemicals, >99%) solution (prepared in DMSO). The mixture then was allowed to react for another 3 h at room temperature under vigorous stirring. Finally, the y-cyclodextrin functionalized GdCDs (y-GdCDs) and CDs (y-CDs) were purified by overnight dialysis in a molecular-grade water.
  • the chemical composition of CDs and GdCDs before and after a modification with y-cyclodextrin was investigated using a Nicolet i S50 fourier transform-infrared (FTIR) advanced KBr gold spectrometer equipped with a Smart iTR diamond ATR device.
  • FTIR Fourier transform-infrared
  • the hydrodynamic size and zeta potential of CDs and GdCDs before and after a modification with y-cyclodextrin were measured using a Malvern Zetasizer Nano ZSP instrument at a temperature of 25 °C.
  • zeta potential and hydrodynamic size measurements the respective samples at a concentration of 0.1 mg mL' 1 were dispersed in 10 mM TES buffer (pH 7) and 0.1% triton x-100, respectively.
  • Quantification of y-cyclodextrin fraction in y-GdCDs The quantification of y-cyclodextrin in y-GdCDs was carried out by studying the interaction of Nile red dye (Sigma- Aldrich), a fluorescent chemical cargo, with y-cyclodextrin. y-cyclodextrin can form an inclusion complex with several chemical cargoes. The interaction of Nile red dye with y- cyclodextrin was investigated by measuring changes in fluorescent intensity of Nile red dye in the presence of y-cyclodextrin.
  • Nile red dye Sigma- Aldrich
  • y-cyclodextrin can form an inclusion complex with several chemical cargoes.
  • the interaction of Nile red dye with y- cyclodextrin was investigated by measuring changes in fluorescent intensity of Nile red dye in the presence of y-cyclodextrin.
  • Nile red dye and y-cyclodextrin Due to poor solubility of Nile red dye and y-cyclodextrin in an aqueous medium, a stock solution of Nile red dye (350 pM) and y-cyclodextrin (400 pM) was prepared in dimethyl sulfoxide (DMSO) (Alfa-Aesar, 99.9%).
  • DMSO dimethyl sulfoxide
  • a 1 mL reaction mixture (30% DMSO in 10 mM (pH 7) TES buffer) containing a fixed amount of dye (15.7 pM) and varying concentrations of y-cyclodextrins (0, 1, 2, 4, 8, 12, 16, 24, 32, and 50 pM) was prepared and incubated for 1 h at room temperature with shaking.
  • the fluorescence spectra were measured after transferring 200 pL from each sample to a 96-well plate and exciting the mixture at 585 nm wavelength. Based on these spectra, a calibration curve was generated by fitting the non-linear relationship between changes in Nile red dye fluorescence intensity (I- lo/Io) and different concentrations of y-cyclodextrin. To quantify the fraction of y- cyclodextrin in y-GdCDs, 100 pg of y-GdCDs was incubated with Nile red dye (15.7 pM) for 1 hour at room temperature with shaking. The fluorescence intensity of the mixture then was measured after exciting at 585 nm and was fitted into the calibration curve to determine the percentage of y-cyclodextrin in y-GdCDs.
  • Soybean (Glycine max) seeds were sown in plastic pots (2.5 x 2.5 x 3.5 mm 3 ) containing standard mixed soil (Sunshine, LC1 mix) and transferred to LED growth chambers (HiPoint). Growth chamber conditions were 250 pmol nr 2 s' 1 PAR, 23/21 °C day/night temp., 60% humidity, and 14/10 h photoperiod. Plants were watered once every two days.
  • the colocalization of y-GdCDs and R6G with chloroplasts in equidistantly separated images in confocal image overlays was performed using the Coloc 2 function in Fiji software.
  • the correlation between the fluorescence signals was analyzed using Pearson’s overlap coefficient analysis. At least three soybean plants were used for CLSM analysis from the leaf surface to deep in the mesophyll cells.
  • Nezara viridula were reared. Briefly, insects were maintained on fresh organic green bean pods (Phaseolus vulgaris L.), raw peanuts (Arachis hypogaea L.), and raw sunflower seeds (Helianthus annuus L.). Late instar nymphs and adults also were provided bouquets of alfalfa plants and soybean plants (Glycine max). All the life stages were maintained in an insectary set at 30°C, 70% relative humidity, and 16-hour photoperiod. [0287] Characterization of N. viridula tarsi. The optical properties of adult insect tarsi were characterized using CLSM.
  • the tarsi were illuminated with lasers at three distinct wavelengths, 355 nm, 488 nm, and 561 nm, and the emitted fluorescence was collected between 400-500, 500-600, and 600-700 nm wavelengths, respectively.
  • the photomultiplier tube (PMT) detection gain was set to 500 and the focal plane pinhole size to 1.5 airy units.
  • the images were acquired using the Zeiss Zen software and processed using Fiji software (Image- J).
  • the tarsal surface of bugs was characterized using a tabletop scanning electron microscope (SEM) (Hitachi TM4000).
  • SEM tabletop scanning electron microscope
  • the tarsi of anesthetized adult insects were cut-off and washed several times with lx phosphate buffer (pH 7.0) to remove the surface contamination.
  • the tarsi then were fixed in formalin for 2 h at room temperature and washed again multiple times with lx phosphate buffer (pH 7.0).
  • the samples were dehydrated in a graded series of ethanol (30, 50, 75, and 95%) and sputter coated with goldpalladium. Finally, the samples were observed under the SEM at an accelerating voltage of 15 KV.
  • Nile red dye was loaded into y-GdCDs nanocarriers using a slight modification of the previously reported method. Briefly, 0.05 mg of Nile red dye was dissolved in 0.425 mL DMSO to prepare the Nile red dye solution, which then was added dropwise to 1 mL of y-GdCDs aqueous dispersion (1 mg) under stirring and left to react for 12 hours at room temperature. The resulting y-GdCDs-Nile red dye composite was dialyzed in water (MWCO: 1 kDa) for 12 hours to remove the free dye.
  • MWCO 1 kDa
  • the quantification of dye in y-GdCDs was determined by transferring 140 pL of the sample to a 96-well plate and mixing with 60 pL DMSO (30% DMSO). The fluorescence intensity of the sample was measured upon excitation at 585 nm and fitted into the calibration curve for the dye quantification.
  • the tarsi were washed three times with 50% acetone (by dipping tarsi for 15 seconds each time) to remove any particles adhering to the tarsal surface.
  • the washed tarsi were embedded in an optimal cutting temperature (OCT) compound and frozen at -20°C inside a cryostat.
  • OCT optimal cutting temperature
  • the frozen sample was used to make 50 pm tarsal sections from the proximal and distal end of the basitarsus (first tarsal segment (T 1 )).
  • the sections then were transferred to microscope slides (Corning 2948- 75x25), mounted with glycerol, covered with coverslips (VWR), and the edges of the coverslip were sealed with nail polish before being observed under an inverted confocal microscope.
  • 250 pL of only Nile red dye solution (containing 7 pg dye) was applied to the insects in a similar way as the y-GdCDs nanocarriers treatment mentioned above.
  • the Nile red dye solution was prepared by transferring 0.1 mL from dye stock solution (2.8 mg mL' 1 , prepared in DMSO) to 9.9 mL of 0.1% triton x-100 solution.
  • the loaded sample was transferred to a separating funnel, and to remove any free Al, the sample was washed by passing 1 mL of dichloromethane (DCM) through the sample three times (Acros Organics, 99.9%).
  • DCM dichloromethane
  • the Al present in the y-CDs were extracted in DCM through liquid-liquid extraction and quantified by a calibration curve generated by measuring the absorbance of insecticide standards at 315 nm using UV-vis spectrophotometer. It is noted that the use of DCM as an extraction solvent is based on the high solubility of the Al in DCM, as indicated by the manufacturer's recommendations.
  • the loading capacity (LC) of nanocarriers was calculated by using the following equation:
  • LC (wt.%) (weight of loaded insecticide/total weight of nanocarrier) x 100% [0293] Nezara viridula mortality assay. The mortality caused by y-CDs-AI was evaluated on freshly harvested soybean leaves. For this study, trifoliate soybean leaves with similar biometric parameters were collected from 20-30-day-old soybean plants that were cultivated in the growth chambers (described herein). To ensure uniformity, the surface area of all the leaves was measured using a portable area meter (LLCOR Biosciences, LI-3000). The collected leaves were transferred to freshly prepared 1% agar (Fisher scientific) plates.
  • the agar media was mixed with 30 ppm of streptomycin (Sigma- Aldrich) and 40 ppm of benzimidazole (Sigma- Aldrich) before pouring.
  • streptomycin Sigma- Aldrich
  • benzimidazole Sigma- Aldrich
  • the agar plates with leaves were randomly divided into 4 different groups, with each group consisting of 10 plates (40 total plates per replicated).
  • Each group was subjected to specific treatments including y-CDs alone, Al alone, y-CDs-AI, and 0.1% triton x-100. Prior to spraying, all the treatment samples were mixed with 0.1% triton x-100.
  • the treatments were applied to the leaves by spraying an optimized volume of 0.7 mL using an airbrush for 15 sec.
  • the amount sprayed was equivalent to having 7 pg Al (10 ppm, an optimized concentration).
  • the leaves were allowed to air dry and then transferred to fresh agar plates to avoid the direct exposure of insects to Al present on the agar surface not covered with leaf.
  • the sprayed amount of Al on leaf surface in both the treatments was calculated to be ⁇ 3 pg.
  • 1-4 days old adult stink bugs were randomly placed in each agar plate, with each group consisting of 10 insects (composed of 5 males and 5 females). The mortality of the stink bugs in each group was determined every 24 h for a period of 96 h. Three independent replications of all treatments were conducted.
  • GdCDs and CDs were coated with boronic acids via the formation of an amide bond between amine groups of CDs and carboxyl groups of 4- carboxyphenyl boronic acid using EDC/NHS coupling.
  • the boronic acid functionalized GdCDs and CDs were tethered covalently to the y-cyclodextrin through the formation of cyclic boronic ester bond between the boronic acid and cis-diols of y-cyclodextrin, resulting in y-GdCDs and y-CDs, respectively.
  • the morphology and thickness of GdCDs and y-GdCDs were analyzed using AFM ( Figure 2B, C).
  • the nanoparticles exhibited spherical shapes with a size distribution in a range of 4-8 nm.
  • the relatively high zeta-potential of GdCDs and CDs showed a value of -23.6 ⁇ 1.1 mV and -37 ⁇ 1.4 mV (TES buffer, pH 7) ( Figure 2E), respectively, can be attributed to the presence of abundant carboxyl groups on their surface.
  • the zeta-potential of y-GdCDs and y-CDs decreased in magnitude to -15 ⁇ 1.2 mV (P ⁇ 0.001) and -12.6 ⁇ 0.7 mV (P ⁇ 0.0001), respectively, similar to previous reports for carbon dot nanocarriers.
  • the fraction of y-cyclodextrin in y-GdCDs and binding to fluorescent chemical cargoes was determined by investigating the host-guest interaction between Nile red dye and y-cyclodextrin.
  • the inventors determined the solubility of Nile red dye in varying DMSO concentrations in aqueous solution through spectrophotometric analysis. With a decrease in DMSO percentages from 100% to 50%, the dye solution showed a red shift in the absorbance maxima (from 550 nm to 582 nm), but without compromising in the absorbance intensity (Figure 9A).
  • the inventors designed nanocarriers and nanoformulations that restrict the translocation across the leaf surface for increasing the availability of active ingredients (Ais) to stink bugs.
  • the cuticle and stomatai pores on the leaf epidermal layer act as the main pathways for the uptake of nanoparticles (NPs) to plant leaves.
  • NPs nanoparticles
  • Various physicochemical properties of NPs, for example, size, charge, hydrophobicity and aspect ratio affect their uptake and translocation in plants.
  • the surfactant surface tension in nanoformulations also affects the uptake of NPs across the leaf surface.
  • y-GdCDs were loaded with R6G dye (y-GdCDs-R6G) ( Figures 10A-10B).
  • Control leaves treated solely with 0.1% triton x-100 displayed no background autofluorescence in the y- GdCDs nanocarrier and R6G emission channels.
  • the leaf cuticle possesses ⁇ 2 nm hydrophilic pores, which may impose a size exclusion limit and prevent the uptake of ⁇ 8 nm size y-GdCDs nanocarriers.
  • the high surface tension of triton x-100 could prevent the uptake of y-GdCDs through stomatai pores into the leaf mesophyll.
  • Repulsion electrostatic interactions between the negatively charged cell walls and negatively charged y-GdCDs may also inhibit nanocarrier translocation across the leaf epidermis.
  • Pectin in plant cell walls has a negative charge, exhibiting a higher affinity towards positively charged NPs that could facilitate their passive translocation acting as a cation exchange membrane.
  • NPs with a charge below +15 mV exhibited less foliar uptake efficiencies into mesophyll tissue.
  • This nanocarrier and nanoformulation design carrying loaded active ingredient (Al) prevents their uptake into soybean leaves making them readily available to stink bugs on the leaf surface.
  • the UV-blue fluorescence indicates exoskeleton structures that predominantly consist of the soft and highly elastic protein known as resilin; whereas green-yellow fluorescence indicates exoskeleton structures composed of weakly or non-sclerotised chitinous material (Figure 4A).
  • the tarsi do not exhibit any autofluorescence in the orange-red fluorescence region (600-700 nm).
  • 50 pm cryostat sections of tarsi show bright autofluorescence at 355 nm and 488 nm excitation wavelengths in UV-blue and green-yellow fluorescence range, but no autofluorescence at 561 nm excitation within the orange-red fluorescence range (Figure 11).
  • This no background fluorescence range offers fluorescence spectra window upon 561 nm excitation for imaging nanocarrier mediated cargo delivery of a fluorescent chemical cargo into the insect tarsi.
  • N viridula tarsi using SEM ( Figure 4B) including the distribution and size of tarsal pores and glands that could act as pathways of the nanocarrier entry through the tarsi.
  • the tarsi of N viridula are composed of three tarsal segments: basitarsus (Tl), mediotarsus (T2), and distitarsus (T3) ( Figure 4B-i).
  • Tl and T3 are larger than the T2 segment, where Tl serves as a hairy adhesive pad with setae on its ventral side.
  • the T3 segment carries a pretarsus (PR) consisting of two curved claws (CL), two pulvilli (P), an unguitractor plate (U), and a pair of paraempodia (PA) ( Figure 4B-ii).
  • PR pretarsus
  • CL curved claws
  • P pulvilli
  • U unguitractor plate
  • PA paraempodia
  • the claws are situated dorsally, while the pulvilli and paraempodia are located ventrally.
  • the paraempodia emerge from the distal surface of the unguitractor plate, whereas the pulvilli originate from the claws.
  • a small plate located at the basal part of each pulvillus is known as the basipulvillus (BP).
  • the ventral surface of the pulvilli appears smooth (Figure 4B-iii), but upon closer examination ( Figure 4B-iv), it becomes apparent that it contains grooves running parallel to the longitudinal axis of the pretarsus.
  • the ventral surface of T1 contains -150 nm sized pores (indicated by red arrows) ( Figure 4B-v), and several pore canals running through the cuticle ( Figure 4B-vi).
  • the inset in Figure 4B-vi shows the presence of clear sub-micron size openings.
  • the ventral side of the pulvillus has also been reported to possess numerous pores on the epicuticle surface.
  • Nile Red dye was chosen for its non-polar nature like many insecticide AIs, and it possesses excitation and emission maxima at 561 nm and 635 nm, respectively, which allowed imaging in the insect tarsi without background autofluorescence (see Figure 4A).
  • T1 for the uptake analysis because this segment along with distal portions of the pulvilli are in direct contact with the leaf surface during stink bug walking, and the highly curved pulvilli impede preparation of sections for imaging.
  • the average fluorescence intensity (n 3) of Nile red dye in both the Nile red and y-GdCDs-Nile red treated insect sections was quantified using ROI manager tools in Image-J software ( Figure 5C).
  • the enhanced uptake could be attributed to the presence of sub-micron sized pores and glands on the tarsal surface (Figure 4B-v,vi), which facilitates greater uptake of nanosized y-GdCDs-Nile red compared to Nile red dye alone. Furthermore, encapsulation of Nile red in y-GdCDs may increase its solubility and thus enhance bioavailability. Similarly, nanocarrier mediated delivery of chemical cargoes has been reported in plant and non-insect animal organisms. The uptake of y-GdCDs in stink bugs was also determined using ICP-OES based on the measurement of the Gd content.
  • the y-CDs- Al After loading the Al, the y-CDs- Al exhibited no notable change in the hydrodynamic size (7.0 ⁇ 0.4 nm) ( Figure 12) and zeta potential (-14.9 ⁇ 1.3 mV) in comparison to y-CDs ( Figures 2D, 2E). This can be attributed to the efficient complexation of Al with y-CDs, without any significant adsorption occurring on the y-CDs surface.
  • the FTIR spectrum of y-CDs-AI shows the appearance of several new peaks that match the peaks of bare Al, in addition to the peaks corresponding to y-CDs ( Figure 13).
  • the formation of the inclusion complex between y-CDs and Al is primarily attributed to hydrophobic interactions between the inner hydrophobic cavity of y-cyclodextrin and the hydrophobic active ingredient (Al).
  • the loading and delivery of hydrophobic Al in y-CDs-AI nanoformulations could improve Al mortality efficacy for N. viridula due to the enhanced solubility and stabilization of the hydrophobic Al.

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Abstract

The disclosure relates to cyclodextrin-modified nanomaterials for carrying insecticides that release such insecticides under controlled conditions.

Description

INSECTICIDE DELIVERY BY NANOCARRIERS
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to U.S. Provisional Patent Application Serial No. 63/603,960 filed on November 29, 2023, the contents of which is incorporated herein by reference in its entirety.
FIELD
[0002] The disclosure relates to cyclodextrin-modified nanomaterials for carrying insecticides that release such insecticides under controlled conditions. The disclosure also relates to methods of delivering insecticides to a plant and treating an insect infestation on the plant by introducing cyclodextrin-modified nanomaterials carrying the insecticides to the plant.
BACKGROUND
[0003] With an expanding global population and the looming threat of climate change impacting crop production, nanotechnology has flourished as a valuable tool to improve sustainable agriculture and provide food security. Although traditional insecticide formulations have been effective in controlling pest populations, in many instances only a small fraction of applied insecticide reach their intended target insects, which often necessitates repeated application the insecticide. Furthermore, the excessive usage of applied insecticides poses a threat to biodiversity, health hazards to farmers and consumers, and leads to the development of insecticide-resistant insect populations. To address this challenge, a transition towards development of targeted insecticide delivery systems is increasingly needed, which can improve the efficacy, safety, and sustainability of pest control management.
BRIEF SUMMARY
[0004] The disclosure provides a conjugate comprising a cyclodextrin conjugated to a nanoparticle, wherein the cyclodextrin comprises a pesticide, optionally an insecticide. [0005] In an embodiment, the pesticide is an insecticide.
[0006] In an embodiment, the nanoparticle is a quantum dot, carbon dot, carbon nanotube, silica nanoparticle, lipid nanoparticle, liposome, metal nanoparticle, metal oxide nanoparticle, or a combination thereof.
[0007] In an embodiment, the nanoparticle is a carbon dot. [0008] In an embodiment, the nanoparticle has an average size of between about 1 nm and 100 nm. The nanoparticle can have an average size of between about 1 nm and 50 nm, 20 nm and 80 nm, 40 nm and 60 nm, or 75 nm and 95 nm in size. The nanoparticle can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53,
54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78,
79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 nm in size. In an embodiment, the nanoparticle has a size of between about 1 nm and 100 nm. The nanoparticle can have a size of between about 1 nm and 50 nm, 20 nm and 80 nm, 40 nm and 60 nm, or 75 nm and 95 nm in size. The nanoparticle can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,
36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60,
61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85,
86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 nm in size.
[0009] In an embodiment, the nanoparticle has an average size of between about 1 and 8 nm, 2 and 9 nm, 5 and 7 nm, 4 and 8 nm, or 3 and 9 nm. The nanoparticle can have a size of between about 1 and 8 nm, 2 and 9 nm, 5 and 7 nm, 4 and 8 nm, or 3 and 9 nm.
[0010] In an embodiment, the nanoparticle has an average size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm. The nanoparticle can have a size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm.
[0011] In an embodiment, the conjugate has an average size of between about 1 nm and 100 nm. The conjugate can have a size of between about 1 nm and 50 nm, 20 nm and 80 nm, 40 nm and 60 nm, or 75 nm and 95 nm in size. The conjugate can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57,
58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82,
83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 nm in size.
[0012] In an embodiment, the conjugate has an average size of between about 1 and 8 nm,
2 and 9 nm, 5 and 7 nm, 4 and 8 nm, or 3 and 9 nm. The conjugate can have a size of between about 1 and 8 nm, 2 and 9 nm, 5 and 7 nm, 4 and 8 nm, or 3 and 9 nm.
[0013] In an embodiment, the conjugate has an average size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm. The conjugate can have a size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm.
[0014] In an embodiment, the cyclodextrin is gamma cyclodextrin. The cyclodextrin can be a beta-cyclodextrin. The cyclodextrin can be an alpha-cyclodextrin. [0015] In an embodiment, the conjugate comprises between about 1-5 cyclodextrins conjugate to a nanoparticle.
[0016] In an embodiment, the conjugate comprises about 3 cyclodextrins conjugate to a nanoparticle.
[0017] In an embodiment, the cyclodextrin forms a molecular cage and the pesticide, optionally an insecticide, is inside the molecular cage.
[0018] In an embodiment, the insecticide is an AChE inhibitors.
[0019] In an embodiment, the AChE inhibitor is aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifosmethyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl □-(methoxyaminothio- phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion- methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion, or a combination thereof.
[0020] In an embodiment, the insecticide is a GABA-gated chloride channel antagonist. [0021] In an embodiment, the GABA-gated chloride channel antagonist is a cyclodiene organochlorine compound, endosulfan, chlordane, phenylpyrazoles, optionally ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole, or a combination thereof.
[0022] In an embodiment, the insecticide is a sodium channel modulator.
[0023] In an embodiment, the sodium channel modulator is a pyrethroid, optionally acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bio-resmethrin, cycloprothrin, cyfluthrin, beta- cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin, metofluthrin, momfluorothrin, epsilon-momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa-tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin, transfluthrin, DDT, methoxychlor, or a combination thereof.
[0024] In an embodiment, the insecticide is a nAChR agonist.
[0025] In an embodiment, the nAChR agonist is a neonicotinoid, acetamiprid, clothianidin, cycloxaprid, dinotefuran, im-idacloprid, nitenpyram, thiacloprid, thiamethoxam; 4,5-dihydro- N-nitro-l-(2-oxiranylmethyl)-lH-imidazol-2-amine, (2E-)-l-[(6-Chloropyridin-3-yl)methyl]- N'-nitro-2-pentylidene_,hydrazine_,carbox_,imidamide; l-[(6-Chloropyridin-3-yl)methyl]-7- methyl-8-nitro-5-propoxy-l,2,3,5,6,7-hexahydro_,imidazo[l,2-a]pyridine; nicotine; sulfoxaflor; flupyradifurone; triflumezopyrim, fenmezoditiaz, flupyrimin, or a combination thereof.
[0026] In an embodiment, the insecticide is a Nicotinic acetylcholine receptor allosteric activator.
[0027] In an embodiment, the Nicotinic acetylcholine receptor allosteric activator is a spinosyn, optionally Spinosad, spineto-ram, or a combination thereof.
[0028] In an embodiment, the insecticide is a chloride channel activator.
[0029] In an embodiment, the chloride channel activator is from the class of avermectins and milbemycins, optionally abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin, or a combination thereof.
[0030] In an embodiment, the insecticide is a juvenile hormone mimic.
[0031] In an embodiment, the juvenile hormone mimic is hydroprene, kino-prene, methoprene; fenoxycarb, pyriproxyfen, or a combination thereof.
[0032] In an embodiment, the insecticide is a Miscellaneous multi-site inhibitor.
[0033] In an embodiment, the Miscellaneous multi-site inhibitor is an alkyl halide including CHsBr, chloropicrin, sulfuryl fluoride, borax, tartar emetic, or a combination thereof.
[0034] In an embodiment, the insecticide is a Chordotonal organ TRPV channel modulator.
[0035] In an embodiment, the Chordotonal organ TRPV channel modulator is afidopyropen, pymetrozine, pyrifluquinazon, or a combination thereof.
[0036] In an embodiment, the insecticide is a mite growth inhibitor.
[0037] In an embodiment, the mite growth inhibitor is clofentezine, hexythiazox, diflovidazin, etoxazole, or a combination thereof.
[0038] In an embodiment, the insecticide is a Microbial disruptors of insect midgut membrane. [0039] In an embodiment, the microbial disruptors of insect midgut membrane is Bacillus thuringiensis, Bacillus sphaericus, and/or the insecticidal proteins they produce, optionally Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Abl, or a combination thereof.
[0040] In an embodiment, the insecticide is an inhibitor of mitochondrial ATP synthase. [0041] In an embodiment, the inhibitor of mitochondrial ATP synthase is diafenthiuron, organotin miticides, optionally azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon, or a combination thereof.
[0042] In an embodiment, the insecticide is an uncouplers of oxidative phosphorylation via disruption of the proton gradient.
[0043] In an embodiment, the uncouplers of oxidative phosphorylation via disruption of the proton gradient is chlorfenapyr, DNOC, sulfluramid, or a combination thereof.
[0044] In an embodiment, the insecticide is a nAChR channel blocker.
[0045] In an embodiment, the nAChR channel blocker is a nereistoxin analogues bensultap, cartap hydrochloride, thio-cyclam, thiosultap-sodium, or a combination thereof.
[0046] In an embodiment, the insecticide is an inhibitor of the chitin biosynthesis type 0. [0047] In an embodiment, the inhibitor of the chitin biosynthesis type 0 is bistrifluron, chlorfluazuron, difluben-zuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, or a combination thereof.
[0048] In an embodiment, the insecticide is an inhibitor of the chitin biosynthesis type 1, optionally buprofezin.
[0049] In an embodiment, the insecticide is a molting disruptor.
[0050] In an embodiment, the molting disruptor is Dipteran, cyromazine, or a combination thereof.
[0051] In an embodiment, the insecticide is an Ecdyson receptor agonist.
[0052] In an embodiment, the Ecdyson receptor agonist is methoxyfenozide, tebufenozide, halofenozide, fufeno-zide, chromafenozide, or a combination thereof.
[0053] In an embodiment, the insecticide is a Octopamin receptor agonist, optionally amitraz.
[0054] In an embodiment, the insecticide is a Mitochondrial complex III electron transport inhibitor. [0055] In an embodiment, the Mitochondrial complex III electron transport inhibitor is hydramethylnon, acequinocyl, fluacrypyrim, bifenazate, or a combination thereof.
[0056] In an embodiment, the insecticide is a METI acaricides and insecticide.: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, rotenone, or a combination thereof.
[0057] In an embodiment, the insecticide is a Voltage-dependent sodium channel blocker: indoxacarb, metaflumizone, 2-[2-(4-cy_,anophenyl)-l-[3- (trifluoromethyl)phenyl]_,ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydra_,zine- carboxamide, N-(3-chloro-2-methyHphenyl)-2-[(4-chlorophenyl)[4-[methyl(methyHsul- fonyl)ami_,no]phenyl]_,methylene]-hydrazinecarboxamide, N-[4-chloro-2-[[(l,l- dimethylethyl)ami_,no]carbo_,nyl]-6-methylphenyl]-l-(3-chloro-2-pyridinyl)-3- (fluoromethoxy)-lH-pyrazole-5-carboxamide, 2-[2-(4-cyanophenyl)-l-[3- (trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide. [0058] In an embodiment, the insecticide is an inhibitor of acetyl CoA carboxylase. [0059] In an embodiment, the inhibitor of acetyl CoA carboxylase is spirodiclofen, spiromesifen, spirotetramat, spiropidion, spirobudifen, 1 l-(4-chloro-2,6-dimethylphenyl)-12- hydroxy-l,4-dioxa-9-azadispiro[4.2.4.2]tetradec-l l-en-10-one, spidoxamat, or a combination thereof.
[0060] In an embodiment, the insecticide is a Mitochondrial complex IV electron transport inhibitor.
[0061] In an embodiment, the Mitochondrial complex IV electron transport inhibitor is aluminum phosphide, calcium phosphide, zinc phosphide, cyanide, or a combination thereof. [0062] In an embodiment, the insecticide is a mitochondrial complex II electron transport inhibitor.
[0063] In an embodiment, the mitochondrial complex II electron transport inhibitor is cyenopyrafen, cyflumetofen, cyetpyrafen, pyflubumide, or a combination thereof.
[0064] In an embodiment, the insecticide is a ryanodine receptor-modulator.
[0065] In an embodiment, the ryanodine receptor-modulator is chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, fluchlordiniliprole, (R)-3-chloro-Nl-{2- methyl-4-[ 1 ,2,2,2-tetrafluoro- 1 -(trifluoro_,methyl)ethyl]phenyl } -N2-(l -methyl-2- methylsulfonylethyl)phthalamid, (S)-3 -chloro-N 1 - {2-methyl-4-[ 1 ,2,2,2-tetrafluoro- 1 - (trifluoromethyl)ethyl]phenyl}-N2-(l-methyl-2-methyl_,sulfonylethyl)phthal_,amide, methyl- 2-[3,5-dibromo-2-({[3-bromo-l-(3-chlorpyridin-2-yl)-lH-pyrazol-5-yl]carbo_,nyl}_,ami- no)benzoyl]-l,2-dimethylhydrazine-carboxylate; N-[2-(5-amino-l,3,4-thiadiazol-2-yl)-4- chloro-6-methyl_,phenyl]-3-bromo-l-(3-chloro-2-pyridinyl)-lH-pyrazole-5-car_,boxamide; 3- chloro- 1 -(3 -chloro-2-pyridinyl)-N-[2,4-dichloro-6-[[( 1 -cyano- 1 -methyHethyl )ami - no]carbonyl]phe_,nyl]-lH-pyrazole-5-carboxamide; tetrachlorantraniliprole; tetraniliprole; tiorantraniliprole; N-[4-chloro-2-[[(l,l-dimethyl_,ethyl)ami_,no]car_,bonyl]-6-methyl- phenyl]-l-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-lH-pyrazole-5-carbox_,amide; cyhalodiamide; N-[2-(5-amino-l,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-l- (3-chloro-2-pyridinyl)-lH-pyrazole-5-carboxamide, or a combination thereof.
[0066] In an embodiment, the insecticide is a Chordotonal organ Modulator, optionally flonicamid.
[0067] In an embodiment, the insecticide is a GABA gated chlorine channel allosteric modulator.
[0068] In an embodiment, the GABA gate chlorine channel allosteric modulator is broflanilide, fluxametamide, isocycloseram, or a combination thereof.
[0069] In an embodiment, the insecticide is Calcium-activated potassium channel modulator, optionally acynonapyr.
[0070] In an embodiment, the insecticide is a Mitochondrial complex III electron transport inhibitor QI site, optionally Flometoquin.
[0071] In an embodiment, the insecticide is Chordotonal organ modulators-undefmed target site, optionally Dimpropyridaz.
[0072] In an embodiment, the insecticide is afoxolaner, azadirachtin, amidoflumet, ben- zoximate, bromopropylate, chino_,methionat, cryolite, cyproflanilid, dicloromezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, mivorilaner, modoflaner, piperonyl butoxide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, 1 l-(4-chl oro-2, 6-dimethylphenyl)-12-hydroxy- l,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-l l-en-10-one, 3-(4’-fluoro-2,4-dimethylbiphenyl-3- yl)-4-hydroxy-8-oxa-l-azaspiro[4.5]dec-3-en-2-one, 4-cyano-N-[2-cyano-5-[[[2,6-dibromo- 4-[l,2,2,3,3,3-hexafluoro-l-(trifluoromethyl)propyl]phenyl]ami_,no]carbonyl]phe_,nyl]-2- methyl-benzamide, 4-cyano-3-[(4-cyano-2-methyl-benzoyl)amino]-N-[2,6-dichloro-4- [l,2,2,3,3,3-hexafluoro-l-(trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide, N-[5-[[[2- chloro-6-cyano-4-[l,2,2,3,3,3-hexafluoro-l-(trifluoromethyl)propyl]phenyl]amino]carbonyl]- 2-cyano-phe_,nyl]-4-cyano-2-methyl-benzamide, N-[5-[[[2-bromo-6-chloro-4-[2,2,2- trifluoro-l-hydroxy-l-(triflu_,oro_,methyl)ethyl]phenyl]amino]carbonyl]-2-cyano-phenyl]-4- cyano-2-methyl-benzamide, N-[5-[[[2-bromo-6-chloro-4-[l,2,2,3,3,3-hexafluoro-l- (trifluoromethyl)pro-pyl]phenyl]ami_,no]carbo_,nyl]-2-cyano-phenyl]-4-cyano-2-methyl- benzamide, 4-cyano-N-[2-cyano-5-[[[2,6-dichloro-4-[l,2,2,3,3,3-hexafluoro-l- (trifluoromethyl)propyl]phenyl]amino]carbonyl]phenyl]-2-methyl-benz_,amide, l-[2-fluoro-
4-methyl-5-[(2,2,2-trifluoro_,ethyl)sulfi_,nyl]phe_,nyl]-3-(trifluoro_,methyl)-lH-l,2,4- triazole-5-amine, N-[5-[[[2-bromo-6-chloro-4-[ 1,2,2, 2-tetrafluoro-l - (trifluoro_,methyl)ethyl]phe-nyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2-methyl- benzamide, 4-cyano-N-[2-cyano-5-[[[2,6-di chi oro-4-[ 1,2,2, 2-tetrafluoro-l-(trifluoro- methyl)ethyl]phenyl]amino]carbonyl]phenyl]-2-methyl-benzamide, actives on basis of bacillus firmus (Votivo, 1-1582); fluazaindolizine; 5-[3-[2,6-dichloro-4-(3,3-dichloroallyl- oxy)phen_,oxy]prop_,oxy]-lH-pyrazole; N-[5-[[2-bromo-6-chloro-4-[l,2,2,3,3,3-hexafluoro- l-(trifluoromethyl)-pro_,pyl]phe_,nyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl- benzamide; 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[l,2,2,3,3,3-hexafluoro-l- (trifluoro^methyl)-propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; 4-cyano-N-[2- cyano-5-[[2,6-di-chloro-4-[l,2,2,2-tetrafluoro-l- (trifluoro_,methyl)ethyl]phenyl]carbamoyl]_,phenyl]-2-methyl-benz_,amide; N-[5-[[2-bromo- 6-chloro-4-[l,2,2,2-tetrafluoro-l-(trifluoromethyl)ethyl]phe-nyl]carb_,a_,mo_yl]-2-cyano- phenyl]-4-cyano-2-methyl-benzamide; 2-(l,3-dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]- pyridine; 2-[6-[2-(5-fluoro-3-pyridinyl)-5-thi_,azo_,lyl]-2-pyridinyl]-pyrimidine; 2-[6-[2-(3- pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; N-methylsuHfonyl-6-[2-(3-pyridyl)thiazol-
5-yl]pyridine-2-carboxamide; N-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2- carboxamide; 1 -[(6-chl oro-3-pyridinyl)methyl]- 1,2, 3,5,6, 7-hexa^hy dro-5-methoxy-7-methyl- 8-nitro-imidazo[l,2-a]pyridine; 1 -[(6-chl oropyridin-3-yl)methyl]-7-methyl-8-nitro- l,2,3,5,6,7-hexahydroimidazo[l,2-a]pyridin-5-ol; N-(3-chloro-2-methylphenyl)-2-[(4- chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide;
1 -[(6-chl oro-3-pyridinyl)methyl]- 1,2, 3,5,6, 7-hexahydro-5-methoxy-7-methyl-8-nitro- imidazo[l,2-a]pyridine; 2-(3-pyridinyl)-N-(2-pyrimidinylmethyl )-2H-indazole-5- carboxamide; tyclopyrazoflor; sarolaner, lotilaner; N-[4-chloro-3-[[(phenyl- methyl)ami_,no]carbo_,nyl]phenyl]- 1 -methyl-3 -(1,1 ,2,2,2-pentafluoroethyl)-4- (trifluoromethyl)-lH-pyrazole-5-carbox_,amide; N-[4-chloro-3- [[(phe_,nylme_,thyl)amino]carbonyl]phenyl]-l-methyl-3-(l, 1,2,2, 2-pentafluoro_,ethyl)-4- (trifluoromethyl)-lH-pyrazole-5-carboxamide; 2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(tri- fluoromethyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3- methyl-6-(trifluoromethyl)imi_,dazo[4,5-b]pyridine; N-[4-chl oro-3 -
(cy cl opropyl_,carb_,amo_yl)phenyl]-2-methyl-5-(l, 1,2,2, 2-pentafluoroethyl)-4- (trifluoromethyl)pyrazole-3-carboxamide, N-[4-chloro-3-[(l- cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-5-(l, 1,2,2, 2-pentafluoroethyl)-4-(trifluoro- me^thyl)pyrazole-3-carboxamide; benzpyrimoxan; tigolaner; oxazosulfyl;
[(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl] N-[4-[l-[4- (trifluoro-methoxy)phenyl]-l,2,4-triazol-3-yl]phenyl]carbamate; [(2S,3R,4R,5S,6S)-3,4,5- trimethoxy-6-methyl-tetrahydropyran-2-yl] N-[4-[ 1 -[4-(trifluoromethoxy)phenyl]- 1 ,2,4- triazol-3-yl]phenyl]carba_,mate; [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy- tetrahydropyran-2-yl] N-[4-[l-[4-(l,l,2,2,2-pentafluoroethoxy)phenyl]-l,2,4-triazol-3- yl]phenyl]carbamate; [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl] N- [4-[l-[4-(l,l,2,2,2-pentafluoroethoxy)phenyl]-l,2,4-triazol-3-yl]phenyl]carbamate; (2Z)-3- (2-isopropylphenyl)-2-[(E)-[4-[l-[4-(trifluoro_,me_,thoxy)phenyl]-l,2,4-triazol-3- yl]phenyl]methylenehydrazono]thiazolidin-4-one, (2Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[l- [4-( 1 , 1 ,2,2,2-pentafluoroethoxy)phenyl]- 1 ,2,4-triazol-3 -yl]phe- nyl]methylenehydrazono]thiazolidin-4-one, (2Z)-3-(2-isopro_,pyl_,phenyl)-2-[(E)-[4-[l-[4- (1,1 ,2,2,2-pen_,tafluoroethoxy)phenyl]- 1 ,2,4-triazol-3 - yl]phenyl]methylenehydrazono]thiazolidin-4-one; 2-(6-chloro-3-ethylsulfonyl-imidazo[l,2- a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imi_,dazo[4,5-b]pyridine, 2-(6-bromo-3- ethylsulfonyl-imidazo[l,2-a]pyridin-2-yl)-3-methyl-6-(tri_,flu_,oro_,methyl)imidazo[4,5- b]pyridine, 2-(3-ethylsulfonyl-6-iodo-imidazo[l,2-a]pyridin-2-yl)-3-methyl-6- (trifluoromethyl)imidazo[4,5-b]pyridine, 2-(7-chloro-3-ethylsulfonyl-imidazo[l,2-a]pyridin- 2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(7-chloro-3-ethylsulfonyl- imidazo[l,2-a]pyri_,din-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(3- ethylsulfonyl-7-iodo-imida_,zo[l,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5- b]pyridine, 3-ethylsulfonyl-6-iodo-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2- yl]imidazo[l,2-a]pyridine-8-carbonitrile, 2-[3-ethylsulfonyl-8-fluoro-6- (trifluoromethyl)imidazo[l,2-a]pyridin-2-yl]-3-methyl-6-(trifluoro_,methyl)imidazo[4,5- b]pyridine, 2-[3-ethylsulfonyl-7-(trifluoromethyl)imidazo[l,2-a]pyridin-2-yl]-3-methyl-6- (trifluoromethylsulfinyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-7-(trifluoromethyl)imi- dazo[l,2-a]pyri din-2 -yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyri dine, 2-(6-bromo-3- ethyHsulfonyl-imidazo[l,2-a]pyridin-2-yl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine; N- [[2-fluoro-4-[(2S,3S)-2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidin-l- yl]phenyl]me_,thyl]cy_,clo_,propanecarboxamide; 2-[2-fluoro-4-methyl-5-(2,2,2- trifluoroethylsulfinyl)phenyl]imino-3-(2,2,2-trifluoroethyl)thiazolidin-4-one; flupentiofenox, N-[3-chloro-l-(3-pyridyl)pyrazol-4-yl]-2-me_,thyl_,sulfonyl-propanamide, cyclobutrifluram; N-[4-chloro-3-[(l-cyanocyclopro_,pyl)carbamoyl]phenyl]-2-methyl-4-methylsulfonyl-5- ( 1,1, 2, 2, 2-pentafluoro_,ethyl)pyrazole-3 -carboxamide, cyproflanilide, nicoflu_,prole; 1,4- dimethyl-2-[2-(pyridin-3-yl)-2h-indazol-5-yl]-l, 2, 4-triazolidine-3, 5-dione, 2-[2-fluoro-4- methyl-5-(2, 2, 2-trifluoroethylsulfa_,nyl)phenyl]imino-3-(2, 2, 2-trifluoroethyl)thi azolidin-4- one, indazapyroxamet, N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylsulfonyl- propanamide, N-cy clopropyl -5 - [(5 S)-5 -(3 , 5 -dHchl oro-4-fl uoro-pheny 1 )-5 -(trifluoromethyl)- 4H-isoxazol-3-yl]isoquino_,line-8-carboxamide, 5-[(5S)-5-(3,5-dichloro-4-fluoro-phenyl)-5- (trifluoromethyl)-4H-isoxazol-3-yl]-N-(pyrimidin-2-ylmethyl)iso_,quinoline-8-carboxamide, N-[l-(2,6-difluorophenyl)pyrazol-3-yl]-2-(trifluoromethyl)benzamide, 5-((lR,3R)-3-(3,5- Bis(trifluoromethyl)phenyl)-2,2-dichlorocyclopropane-l-carboxamido)-2-chloro-N-(3-(2,2- difluoroacetamido)-2,4-difluorophenyl)benzamide, l-[6-(2,2-difluoro-7-methyl- [l,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile, 6- (5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro-7-methyl-[l,3]dioxolo[4,5- f]benzimidazole, or a combination thereof.
[0073] In an embodiment, the insecticide is acephate, fipronil, cypermethrin, bifenthrin, tefluthrin, cyhalothrin, clothianidin, dinotefuran, imidacloprid, thiacloprid, thiamethoxam, sulfoxalor, spinosad, spientoram, emamectin, abamectin, pymetrozine, flonicamid, chlorfenapyr, buprofezin, metaflumizone, cyflumetofen, chlorantraniliprole, tetraniliprole, cyantraniliprole, tiorantraniliprole, pioxaniliprole, fluchlordiniliprole, afidopyropen, dimpropyridaz, fenmezoditiaz, sulfiflumin, broflanilide, cyproflanilide, mivorilaner, modoflaner, umifoxolaner, isocycloseram, indazapyroxamet, spidoxamat, spirotetramat, any insecticide, or biochemical insecticide, or a combination thereof.
[0074] In an embodiment, the cyclodextrin is a molecular basket.
[0075] In an embodiment, the cyclodextrin is conjugated to a nanoparticle by a linker.
[0076] In an embodiment, the linker is 4-caryboxylphenyl boronic acid (CBPA).
[0077] In an embodiment, the linker is 4-aminophenylboronic acid.
[0078] In an embodiment, a composition can comprise an effective amount of a conjugate comprising a cyclodextrin conjugated to a nanoparticle, wherein the cyclodextrin comprises a pesticide, optionally an insecticide.
[0079] In an embodiment, the composition further comprises diluents, preservatives, organic solvents, solubilizers, emulsifiers, surfactants, dispersants, preservatives, colorants, fillers, diluents, binders, glidants, lubricants, disintegrants, anti-adherents, sorbents, coatings, wetting agents, penetrants, vehicles, or a combination thereof.
[0080] In an embodiment, the composition is formulated as a liquid, powder, suspension, paste, pellet, or gel. [0081] In an embodiment, the insecticide is present in an amount ranging from 0.001 to 10,000 ppm, 0.1 to 2000 ppm, or 1 to 1000 ppm.
[0082] In an embodiment, a method of treating a plant can comprise contacting a plant with an effective amount of a conjugate or composition comprising a cyclodextrin conjugated to a nanoparticle, wherein the cyclodextrin comprises a pesticide, optionally an insecticide.
[0083] In an embodiment, the plant is suffering from a pest infestation, optionally an insect infestation, a nematode infestation, an arachnid infestation, or a combination thereof.
[0084] In an embodiment, a method of pest control of a plant can comprise contacting a plant with an effective amount of a conjugate or composition comprising a cyclodextrin conjugated to a nanoparticle, wherein the cyclodextrin comprises a pesticide, optionally an insecticide.
[0085] In an embodiment, the pesticide is an insecticide.
[0086] In an embodiment, the pest is an insect, an arachnid, a nematode, or a combination thereof.
[0087] In an embodiment, the insect is from the order Lepidoptera.
[0088] In an embodiment, the insect is Helicoverpa spp., Heliothis virescens, Lobesia botrana, Ostrinia nubilalis, Plutella xylostella, Pseudoplusia includens, Scirpophaga incertulas, Spodoptera spp., Trichoplusia ni, Tuta absoluta, Cnaphalocrocis medialis, Cydia pomonella, Chilo suppressalis, Anticar sia gemmatalis, Agrotis ipsilon, Chrysodeixis includens, or a combination thereof.
[0089] In an embodiment, the insect is from the order Hemiptera.
[0090] In an embodiment, the insect is selected from Lyguss spp.
[0091] In an embodiment, the insect is a stink bug.
[0092] In an embodiment, the insect is Euschistus spp., Halyomorpha halys, Nezara viridula, Piezodorus guildinii, Dichelops furcatus, or a combination thereof.
[0093] In an embodiment, the insect is a thrip.
[0094] In an embodiment, the insect is Frankliniella spp., Thrips spp., Dichromothrips corbettii, or a combination thereof.
[0095] In an embodiment, the insect is an aphid.
[0096] In an embodiment, the insect is Acyrthosiphon pisum, Aphis spp., Myzus persicae, Rhopalosiphum spp., Schizaphis graminum, Megoura viciae, or a combination thereof.
[0097] In an embodiment, the insect is a whitefly.
[0098] In an embodiment, the insect is Trialeurodes vaporariorum, Bemisia spp., or a combination thereof. [0099] In an embodiment, the insect is from the order Coleoptera.
[00100] In an embodiment, the insect is Phyllotreta spp., Melanotus spp., Meligethes aeneus, Leptinotarsa decimlineata, Ceutorhynchus spp., Diabrotica spp., Anthonomus grandis, Atomaria linearia, Agriotes spp., Epilachna spp., or a combination thereof.
[0100] In an embodiment, the insect is a fly.
[0101] In an embodiment, the insect is Delia spp., Ceratitis capitate, Bactrocera spp., Liriomyza spp., or a combination thereof.
[0102] In an embodiment, the insect is from the order Coccoidea.
[0103] In an embodiment, the insect is Aonidiella aurantia, Ferrisia virgate, or a combination thereof.
[0104] In an embodiment, the pest is from the order Arachnida.
[0105] In an embodiment, the pest is Penthaleus major, Tetranychus spp., or a combination thereof.
[0106] In an embodiment, the pest is a nematode.
[0107] In an embodiment, the pest is Heterodera glycines, Meloidogyne sp., Pratylenchus spp., Caenorhabditis elegans, or a combination thereof.
[0108] In an embodiment, the pest is a member of the Pentatomidae family.
[0109] In an embodiment, the pest infestation is on a leaf, stem, root, or a combination thereof.
[0110] In an embodiment, the pesticide, optionally an insecticide enters through the insect tarsi, optionally tarsal pores. The insecticide can enter through the insect tarsi, optionally tarsal pores.
[OHl] In an embodiment, the pesticide, optionally an insecticide, does not significantly penetrate the cuticle of the plant. In an embodiment, the insecticide does not significantly penetrate the cuticle of the plant.
BRIEF DESCRIPTION OF THE DRAWINGS
[0112] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
[0113] The drawings are submitted in duplicate, a color version and a grayscale version. The numbering for the drawings are the same and the descriptions are the same.
[0114] Figure 1 depicts the targeted carbon dot based nanocarriers for the delivery of chemical cargoes to stink bugs (Nezara viridula). Nanocarriers, composed of carbon dots (CDs) with molecular baskets (y-cyclodextrins), were specifically designed with size and charge properties that facilitate their spontaneous translocation through the stink bug leg tarsal surface and effectively reduce the delivery of chemical cargoes through the plant leaf surface. The inventors used Gds doping of CDs (GdCDs) to detect nanocarriers by elemental analysis in stinkbugs. The fluorescence properties of the CDs and their chemical cargoes allows high resolution imaging by confocal microscopy. This nanotechnology-based approach offers the potential to enhance the delivery efficiency of insecticide active ingredients, while simultaneously reducing losses in the environment.
[0115] Figures 2A-2J depicts the characterization of nanocarriers made of carbon dots and molecular baskets and loading of fluorescent chemical cargo. (Figure 2A) Schematic depicts the steps for y-cyclodextrin modifications of GdCDs (y-GdCDs) and CDs (y-CDs). (Figure 2B) AFM image of GdCDs and (Figure 2C) y-GdCDs with their height profile. (Figures 2D- 2H) Hydrodynamic size (Figure 2D), zeta potential (Figure 2E), FTIR spectra (Figure 2F), absorbance spectra (Figure 2G), and fluorescence spectra (Figure 2H) of GdCDs and CDs before and after modifications with y-cyclodextrin. (Figure 21) Fluorescence spectra of Nile red dye in the presence of different concentrations of y-cyclodextrin, excited at 585 nm. (Figure 2J) Calibration curve showing nonlinear fitting between Nile red fluorescence intensity changes (I-Io/Io) and different concentrations of y-cyclodextrin (n = 3). I and Io represent the fluorescence intensities of Nile red in the presence and absence of y- cyclodextrin, respectively.
[0116] Figures 3A-3C depicts the nanocarrier and chemical cargo interactions with plant leaf surface. (Figures 3 A) Confocal images of leaves after 3 h incubation with nanocarriers. Cyan indicates y-GdCDs fluorescence (Ex. k- 355 nm), yellow indicates R6G dye fluorescence (Ex. - 488 nm), and magenta indicates chloroplast autofluorescence. Green indicates the colocalization of y-GdCDs with R6G dye. Both orthogonal (Figures 3B) and 3D views (Figures 3C) of representative confocal z-stacks displaying no colocalization of nanocarrier and dye with chloroplasts in leaf mesophyll cells but shows colocalization of y- GdCDs with R6G dye (n = 3). This lack of colocalization indicates that the nanocarriers and their chemical cargoes do not enter the soybean leaves and are readily available to stink bugs on the leaf surface. Scale bar = 50 pm.
[0117] Figures 4A-4B depicts the optical and physical properties of stink bug tarsi. (Figure 4 A) Confocal images of N. viridula tarsi show autofluorescence after excitation at 355 nm and 488 nm wavelengths, but not at 561 nm excitation wavelength (scale bar = 250 pm). (Figure 4B) SEM images of N viridula tarsi, (i) Ventral view of three tarsal segments (Tl- T3) and pretarsus (PR), (ii) Ventral view of PR showing an unguitractor plate (U), basipulvillus (BP), two pulvilli (P), two curved claws (CL), and two parapodia (PA), (iii-vi) High magnification images of pulvilli (iii,iv) and T1 (v,vi). Black arrows indicate the pores present on the tarsal surface. Inset in (vi) shows the magnified image of glands highlighted in black circles.
[0118] Figures 5A-5B depict the fluorescent chemical cargo delivery to stink bugs tarsi by nanocarriers. (Figure 5 A) Steps to determine the uptake of Nile red delivered by y-GdCDs nanocarriers to N. viridula tarsi via confocal microscopy. (Figure 5B) Confocal images of tarsi sections (Tl) prepared from proximal and distal ends show the uptake of Nile red dye delivered by y-GdCDs nanocarriers (n = 3). Blue indicates the tarsi autofluorescence (Ex. = 488 nm) and red indicates Nile red dye fluorescence (Ex. A = 561 nm) (scale bar = 50 pm). (C) Quantitative average fluorescence intensity of Nile red delivered without and with y- GdCDs nanocarriers. Asterisks indicate significant differences between y-GdCDs-Nile red and only Nile red (independent t-test, **P <0.05). (D) Uptake of nanocarriers by the stinkbug tarsi was determined by the ICP-OES analysis of Gd from the y-GdCDs core (n = 3).
[0119] Figures 6A-6D depict the efficacy of nano formulation on N. viridula mortality. (Figure 6A) Cumulative mortality of Nezara viridula caused by Al delivered in y-CDs compared to Al alone, y-CDs alone, and 0.1% triton-x 100 alone. (Figure 6B) Toxicity of Al delivered by y-CDs compared to Al alone and y-CDs alone on bugs after removing their stylets. Each treatment contained 10 bugs on 10 leaves in separate petri dishes and the treatments were replicated 3 times. Asterisks in A and B indicate significant differences between insect mortality caused by y-CDs-AI and Al alone (Tukey's post hoc test, **P < 0.001 and ****P <0.0001). (Figure 6C) Comparative analysis of stink bug mortality caused by y-CDs- Al on whole insects and insects after removal of their stylets. (Figure 6D) Comparative analysis of stink bug mortality caused by Al alone on whole insects and insects after removal of their stylets. Asterisks in C and D indicate significant differences in insect mortality caused by each treatment group, (independent t-test, *P = 0.0129, **P = 0.0011, ***P = 0.0002, and ****P < 0.0001).
[0120] Figure 7A depicts a schematic depicting the stepwise synthesis of y-cyclodextrin modified GdCDs (y-GdCDs), and Figure 7B depicts a schematic depicting the stepwise synthesis of CDs (y-CDs).
[0121] Figure 8A depicts the absorbance of CDs and y-CDs showed two absorbance peaks at 334 nm and 394 nm and Figure 8B depicts the fluorescence spectra of CDs and y-CDs showed fluorescence emission maxima at 450 nm. [0122] Figure 9A depicts the absorbance spectra of Nile red dye in the presence of different percentages of dimethyl sulfoxide (DMSO) in deionized water. Figure 9B depicts the solubility of dye in different percentages of DMSO in deionized water.
[0123] Figure 10A depicts the absorbance of y-GdCDs, R6G, and y-GdCDs-R6G. The spectra of y-GdCDs-R6G shows that in addition to the y-GdCDs peak at 350 nm, a new peak at 525 nm appeared, which matches with the R6G absorbance peak (inset shows the clear R6G absorbance peak at 525 nm in y-GdCDs-R6G). Figure 10B depicts the fluorescence spectra of y-GdCDs, R6G, and y-GdCDs-R6G. The spectra of y-GdCDs upon excitation at 525 nm, does not show any emission peak. Whereas the spectra of y-GdCDs-R6G composite showed the appearance of an emission peak at 552 nm, which matches with the only R6G emission peak. Together both absorbance and fluorescence measurements confirm the interaction of R6G with nanocarriers.
[0124] Figure 11 depicts the confocal images of tarsal sections (Tl) prepared from proximal and distal end show autofluorescence after excitation at 355 nm and 488 nm wavelengths, but no excitation at 561 nm (scale bar = 50 pm).
[0125] Figure 12 depicts the hydrodynamic size and zeta potential of y-CDs-AI (n = 3).
[0126] Figure 13 depicts the FTIR spectrum of y-CDs alone, Al alone, and y-CDs-AI. The FTIR spectrum of y-CDs-AI showed the appearance of several new peaks that match the peaks of bare Al, in addition to the peaks corresponding to y-CDs.
[0127] Figure 14 depicts photographs of experimental set-up showing four different treatment groups used in mortality experiments.
[0128] Figure 15 Mantel-Cox pairwise comparison between the survival of stink bugs after treatment with Al alone and y-CDs-AI. The significant difference was calculated at a confidence level of 95% (*P = 0.033) using Kaplan-Meier statistics.
[0129] Figures 16A-16B depict photographs of stink bugs with and without stylet. (Figure 16A) Photographs of stink bugs with stylet. (Figure 16B) Photographs of stink bugs without stylet. Black arrow in (A) shows the presence of needle like stylet, whereas (B) shows the absence of the stylet.
[0130] Figure 17 depicts a digital photograph of a soybean leaf placed on a 1% agar plate reveals the presence of moisture on leaf surface, which can serve as a medium for the uptake of nanocarrier present on leaf surface by the stink bugs, potentially through their tarsi. DETAILED DESCRIPTION
[0131] Definitions
[0132] “Insecticide,” as used herein, refers broadly to a chemical agent used to kill or inhibit a pest and/or pathogen. Pests include, but are not limited to, arthropods, optionally, insects, arachnids, and their larvae and eggs. In an embodiment, the pest is a stink bug. Pathogens include, but are not limited to, fungi, viruses, and bacteria. A pest could be a transmission vector for a pathogen. Inhibition of a pest and/or a pathogen could promote the health and/or growth of a plant, and/or treat a disease of a plant infested or infected by a pest and/or a pathogen. An “insecticide” can be a natural or synthetic organic compound. The insecticide can be an anti-microbial agent, for example, a fungicide or bactericide (, optionally, antibiotic agent).
[0133] “Functionalized” or “functionalization,” as used herein, refers broadly to a compound or material (, optionally, a nanoparticle) that has been modified to confer additional function to the compound or material (, optionally, a function of targeting or a function of having enhanced cargo loading capacity). For example, a nanoparticle can be functionalized by linking a gamma-cyclodextrin and/or molecular basket to its surface. [0134] “Linked,” as used herein, refers broadly to a linkage of two elements in a functional relationship. For example, “linked” can refer to a linkage of an insecticide and a targeting agent in a functional relationship. The term “linked” also refers to the linkage/association of two chemical moieties so that the location or biodistribution of one might be affected by the other. For example, an insecticide is said to be "linked to" or "associated with" a targeting moiety, wherein after the introduction of an insecticide to a plant in need thereof, the cargo’s transport/biodistribution into and within the plant is affected by the linked targeting moiety. Thus, as used herein, the functional relationship between the cargo and the linked targeting moiety can involve co-transportation and/or colocalization within certain plant compartments (, optionally, leaf, stem, root, or vasculature, e.g., phloem). [0135] “Introduce,” as used herein, refers broadly to contacting a plant, or a portion thereof, with a material (, optionally, a conjugate described herein). For example, a conjugate or a composition comprising the conjugate can be applied to the plant, or a portion thereof (, optionally, leaf or spore). The plant, or a portion thereof (, optionally, foliage and/or other tissues), is sprayed with the conjugate or a composition comprising the conjugate. The plant, or a portion thereof, is coated with the conjugate or a composition comprising the conjugate (, optionally, a leaf dipped in a composition). The conjugate or a composition comprising the conjugate is administered to the plant (, optionally, via injection). [0136] “Effective amount,” as used herein, refers broadly to an amount of a conjugate as described herein to inhibit a pest and/or pathogen.
[0137] Controlled Delivery of Insecticides
[0138] The delivery of insecticides to plants, including food crops, can be challenging. It is preferred that the insecticide delivery be specific and in limited quantities. The United Nations established zero hunger by 2030 as a sustainable development goal to achieve food security. United Nations Statistics Division. Goal 2: End hunger, achieve food security and improved nutrition and promote sustainable agriculture. Stink bugs (Hemiptera Pentatomidae) are a major pest of food crops affecting over 60 different crop varieties worldwide and causing annual crop losses that can surpass those caused by other insects. Karar, H. et al. Saudi J. Biol. Sci. 28, 3477-3482 (2021); Williams, M. R. Cotton insect losses 2005. in Proceedings of the Beltwide Cotton Conferences, National Cotton Council, Memphis, TN, USA 1151-1204 (2006); McPherson, J. E. & McPherson, R. Stink Bugs of Economic Importance in America North of Mexico. (CRC Press, 2000).
[0139] Soybean (Glycine max L.) is an important crop affected by the southern green stink bug (Nezara viridula L), and accounting for 53% of the world’s oilseed crops. Giacometti, R. et al. Sci. Rep. 10, 15468 (2020); Pratap et al. Chapter 12 - Soybean, in Breeding Oilseed Crops for Sustainable Production (ed. Gupta, S. K.) 293-315 (Academic Press, 2016); Nair et al. Global Status of Vegetable Soybean. Plants 12, (2023). This stink bug causes damage to soybean foliage and beans by using their piercing-sucking stylets to inject digestive enzymes into the plant tissue and sucking their fluids. This results in loss of turgidity, delayed maturation, stunted growth, and undersized or aborted seeds. The primary strategy for managing N. viridula population worldwide relies on the use of synthetic insecticides including systemic insecticides (optionally, neonicotinoids) and non-systemic insecticides (optionally, pyrethroids). The main exposure routes of stink bugs to insecticides are possibly from tarsal and oral exposure, depending on where the insecticide locates. Although traditional insecticide formulations have been effective in controlling their population, only a small fraction of applied insecticide active ingredient (Al) reach their intended target insects, which often necessitates repeated insecticide application. To address this challenge, a transition towards development of targeted insecticide delivery systems is increasingly needed, which can improve the efficacy, safety, and sustainability of pest control management.
[0140] With an expanding global population and the looming threat of climate change impacting crop production, nanotechnology has flourished as a valuable tool to improve sustainable agriculture and provide food security. Nanomaterials (NMs) hold great promise in the development of new technologies and strategies for crop pest management. Their unique physicochemical properties have been explored for controlled and targeted delivery applications in plants, presenting a tremendous potential to improve the insecticide efficiency while reducing their environmental impact. NMs delivery efficiency can be adjusted by manipulating their size, charge, surface area, and polarity. NMs penetration through the insect cuticle. Insecticide active ingredient (Al) delivery is increased by nanocarriers to the stink bugs via tarsal pores as a route for the Al delivery in insects that would enhance mortality. [0141] Carbon dots (CDs) are preferred for delivery applications due to their unique properties of facile synthesis, small size, high aqueous solubility, internal fluorescence properties, biocompatibility, and degradability. CDs have a beneficial effect on various plant physiological processes, including on growth, photosynthesis, and resistance to biotic/abiotic stress. The surface functional groups present on CDs make them easily modifiable, enabling CDs as excellent nanocarriers for targeted delivery of chemical cargoes.
[0142] Cyclodextrins, a class of non-toxic cyclic molecules made up of glucose units linked by a 1-4 glycosidic bonds, is a versatile tool for constructing smart nano-delivery systems in combination with other nanomaterials. These molecular baskets with a hydrophobic internal cavity form an inclusion complex with hydrophobic compounds improving solubilization, slow release, reduced active ingredient (Al) evaporation, and stability in formulations of a wide range of chemicals. Therefore, by incorporating insecticide Al into cyclodextrin- modified CDs, the inventors surprisingly discovered that it improved their delivery and increase their efficacy against stink bugs. Carbon dot nanocarriers with molecular baskets have been studied for chemical cargo delivery in plants but not in insect pests.
[0143] The inventors surprising found that y-cyclodextrin-modified carbon dots (y-CDs) act as a nanocarrier to deliver insecticide Al into the tarsi of stink bugs (N. viriduld), thereby increasing their efficacy and insect mortality. The physicochemical properties of these nanocarriers after foliar application were designed to restrict their uptake through to the leaf surface, allowing the nanocarrier to contact and enter the bugs via the sub-micron sized pores present in their tarsi as they walk on the leaf surface (Figure 1). The inventors demonstrated proof of concept of tarsal delivery of nanocarriers with y-cyclodextrin functionalized Gd3+- doped CDs (y-GdCD). The fluorescence emitting properties of y-GdCD allowed tracking of their interactions in soybean leaves by confocal microscopy. The uptake of nanocarriers to stink bugs through their tarsi and their ability to deliver the chemical cargoes was demonstrated with ICP-OES analysis of y-GdCD and confocal microscopy of y-GdCD loaded with Nile red dye, respectively. For agricultural applications, an undoped y-CDs nanocarrier with comparable physiochemical properties to y-GdCD was synthesized and loaded with insecticide Al (y-CDs-AI) to demonstrate the efficacy of y-CDs-AI nano-formulation increasing stink bug mortality.
[0144] Cyclodextrin-Carbon Dot-Insecticide Conjugates
[0145] The inventors developed carbon dot-based nanocarriers (y-CDs-AI) for the enhanced delivery and efficacy of an insecticide to stink bug N. viridula through the tarsi. The physicochemical properties of the nanocarrier maximizes the nano-formulation levels on the soybean leaf surface, allowing it to enter the stink bugs via sub-micron size pores in their tarsi as they walk on the leaf surface. Elemental and confocal microscopy analysis indicated that y-GdCDs are uptaken through the insect tarsi and the delivery of Nile red is enhanced 2.6 times by the nanocarriers. The y-CDs-AI increased the solubility of the hydrophobic active ingredient (Al) cargoes making it a more efficient formulation for crop protection against pests. Nanocarrier mediated delivery of the active ingredient (Al) resulted in 25% higher mortality in stink bugs than the active ingredient (Al) alone. Syletectomy studies indicated Al delivery through the tarsi by y-CDs-AI having -45% higher mortality compared to Al alone in insects with stylets removed. The y-CDs-AI had a similar mortality regardless of stylet removal while Al alone showed 20% lower mortality in insects with their stylet removed. Carbon dot based nanocarriers are a promising and sustainable approach for significantly enhancing the delivery and efficacy of insecticide active ingredient (Al) through a novel non- classical route. The development of y-CDs-AI enabling a more precise delivery of Al on the leaf surface in direct contact with insect pests can lead to significant reductions in overall Al needed to manage N viridula and other insects that have tarsal pores.
[0146] The disclosure provides a conjugate comprising a cyclodextrin linked to an insecticide. In an embodiment, the disclosure provides a conjugate comprising a cyclodextrin linked to an pesticide, optionally an insecticide. The cyclodextrin can be gamma-cyclodextrin. Nanocarriers, composed of carbon dots (CDs) with molecular baskets (y-cyclodextrins), were specifically designed with size and charge properties that facilitate their spontaneous translocation through the insect leg tarsal surface and effectively reduce the delivery of the insecticide through the plant leaf surface.
[0147] A conjugate described herein can comprise a cyclodextrin linked to an insecticide. The insecticide may be linked directly or indirectly. [0148] A conjugate described herein can comprise a cyclodextrin linked to a pesticide, optionally an insecticide. The pesticide, optionally an insecticide, can be linked directly or indirectly.
[0149] The conjugate can comprise a nanoparticle, wherein the nanoparticle is a quantum dot, carbon dot, carbon nanotube, silica nanoparticle, optionally porous silica nanoparticle, lipid nanoparticle, liposome, metal or metal oxide nanoparticle, a micro nutrient-based nanoparticle, macro nutrient-based nanoparticle, or a combination thereof. The nanoparticle can be linked to a cyclodextrin. The nanoparticle can be linked to gammacyclodextrin. The insecticide can be linked to the nanoparticle.
[0150] A conjugate described herein can comprise a cyclodextrin linked to a nanoparticle, wherein the conjugate is capable of being delivered to a plant, and the nanoparticle is a quantum dot, carbon dot, carbon nanotube, silica nanoparticle, optionally a porous silica nanoparticle, lipid nanoparticle, liposome, metal or metal oxide nanoparticle, and micro nutrient-based nanoparticle, macro nutrient-based nanoparticle, or a combination thereof. [0151] The conjugate described herein can comprise a cyclodextrin linked to an insecticide.
[0152] Nanoparticles
[0153] The nanoparticle can be a quantum dot, carbon dot, carbon nanotube, silica nanoparticle, optionally porous silica nanoparticle, lipid nanoparticle, liposome, metal or metal oxide nanoparticle, a micronutrient-based nanoparticle, macro nutrient-based nanoparticle, or a combination thereof. The nanoparticle can be a carbon dot (CD).
[0154] The nanoparticle can be a quantum dot, carbon dot, carbon nanotube, optionally a single walled carbon nanotube (SWCNT), silica nanoparticle, lipid nanoparticle, liposome, metal nanoparticle, metal oxide nanoparticle, and a micro nutrient-based nanoparticle, macro nutrient-based nanoparticle, or a mixture thereof.
[0155] The carbon nanotube can be a single walled carbon nanotube (SWCNT).
[0156] The silica nanoparticle can be a porous silica nanoparticle.
[0157] The silica nanoparticle can be a mesoporous silica nanoparticle.
[0158] The nanoparticle is a metal or metal oxide nanoparticle (optionally, gold, silver, copper, zinc, zinc oxide, magnesium, magnesium oxide, cerium oxide, or iron oxide nanoparticle). The nanoparticle is not a metal or metal oxide nanoparticle (optionally, gold, silver, or iron oxide nanoparticle).
[0159] The nanoparticle can be a carbon dot comprising metal (optionally, metal doped carbon dot). The nanoparticle can be a carbon dot that does not comprise metal. [0160] The metal nanoparticle can be a gold, silver, copper, zinc, magnesium nanoparticle, or a mixture thereof.
[0161] The metal oxide nanoparticle can be a copper oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide nanoparticle, or a mixture thereof.
[0162] The micro nutrient-based nanoparticle can comprise nitrogen, phosphorus, copper, zinc, magnesium, or a mixture thereof.
[0163] The macro nutrient-based nanoparticle can comprise nitrogen, phosphorous, copper, zinc, magnesium, or a mixture thereof.
[0164] The nanoparticle can be between about 1 nm to 100 nm in size, optionally have a size distribution of between about 1 nm to 10 nm in size. The nanoparticle can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm in size. For example, the nanoparticle can have a size of between about 1-9 nm, 2-8 nm, 2-7 nm, 3-6 nm, 4-5 nm, 1-4 nm, 2-3 nm, 1-2.5 nm, 4-8 nm, or 3-7 nm. [0165] The nanoparticle can have an average size distribution of between about 1 nm and 10 nm. The nanoparticle can have an average size distribution of between about 1 and 8 nm, 2 and 9 nm, 5 and 7 nm, 4 and 8 nm, or 3 and 9 nm. The nanoparticle can have an average size distribution of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm.
[0166] The nanoparticle can have an average size of between about 1 and 100 nm, for example, the nanoparticle can have an average size of between about 1 nm and 50 nm, 20 nm and 80 nm, 40 nm and 60 nm, or 75 nm and 95 nm. The nanoparticle can have an average size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 nm.
[0167] The nanoparticle can be between about 1 and 100 nm in size, for example, the nanoparticle can have a size of between about 1 nm and 50 nm, 20 nm and 80 nm, 40 nm and 60 nm, or 75 nm and 95 nm in size. The nanoparticle can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,
36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60,
61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85,
86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 nm in size.
[0168] The nanoparticle can be spherical or non- spherical. Methods for characterizing nanoparticles or nanomaterials are known in the art and are described herein (optionally, electron microscopy, dynamic light scattering, transmission electron microscopy (TEM), or atomic force microscopy).
[0169] The nanoparticles can have spherical shapes with a size distribution in a range of about 4-8 nm.
[0170] The nanoparticle surface (optionally, a carbon dot, see Figure 1) can be dualfunctionalized with a cyclodextrin molecular basket, wherein insecticide loaded in the cyclodextrin molecular basket.
[0171] The nanoparticle can be a micro or macro nutrient-based nanoparticle that could serve as a nano-fertilizer that supplements a plant with micro or macro nutrient(s) (optionally, nitrogen, phosphorus, copper, zinc, or magnesium). The nanoparticle can be a phosphorus nano-fertilizer, e.g., nano-sized hydroxyapatite (Cas(PO4)3OH). The nanoparticle can be a urea-modified hydroxyapatite nanoparticle.
[0172] Surface modification methods for nanoparticles (optionally, hydroxyapatite, metal, or metal oxide nanoparticles) are known in the art and described herein. The surface of a hydroxyapatite, metal or metal oxide nanoparticle can have a layer of silica coating (SiCh). The surface of a hydroxyapatite, metal or metal oxide nanoparticle can be functionalized with a linker described herein including a silane-based molecule or a polymer, e.g., PEG that could be further functionalized with a gamma-cyclodextrin as described herein.
[0173] The nanoparticle can have a zeta potential magnitude of about 10 mV to 60 mV.
[0174] Insecticides
[0175] The insecticide can be a small molecule compound having a molecular weight of less than 1000 g/mol. The insecticide can be a small molecule having a molecular weight of less than 800 g/mol. The insecticide can be a small molecule having a molecular weight of less than 700 g/mol. The insecticide can be a polypeptide or polynucleotide that kills or inhibits a pest. The conjugate can optionally comprise a pesticide.
[0176] The following is a non-exhaustive list of insecticides and pesticides that can be included in an embodiment of the disclosure. Embodiments of the disclosure can include one or more insecticides, including one or more of the following insecticides. The following insecticides are grouped according to the Mode of Action Classification of the Insecticide Resistance Action Committee (IRAC):
[0177] AChE inhibitors: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifosmethyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion, or a combination thereof.
[0178] GABA-gated chloride channel antagonists: cyclodiene organochlorine compounds: endosulfan, chlordane; phenylpyrazoles: ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole, or a combination thereof.
[0179] Sodium channel modulators: pyrethroids, optionally acrinathrin, allethrin, d-cis- trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S- cylclopentenyl, bio-resmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta- cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin,metofluthrin, momfluorothrin, epsilon-momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa-tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin, transfluthrin, DDT, methoxychlor, or a combination thereof.
[0180] nAChR agonists: neonicotinoids: acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; 4,5-dihydro-N-nitro-l-(2- oxiranylmethyl)-lH-imidazol-2-amine, (2E-)-l-[(6-Chloropyridin-3-yl)methyl]-N'-nitro-2- pentylidenehydrazinecarboximidamide; l-[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 5-propoxy-l,2,3,5,6,7-hexahydroimidazo[l,2-a]pyridine; nicotine; sulfoxaflor; flupyradifurone; triflumezopyrim, fenmezoditiaz, flupyrimin, or a combination thereof.
[0181] Nicotinic acetylcholine receptor allosteric activators: spinosyns, optionally spinosad or spinetoram. [0182] Chloride channel activators from the class of avermectins and milbemycins, optionally abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin, or a combination thereof.
[0183] Juvenile hormone mimics, for example, hydroprene, kino-prene, methoprene; fenoxycarb, pyriproxyfen, or a combination thereof.
[0184] Miscellaneous multi-site inhibitors: an alkyl halide including CHsBr, chloropicrin, sulfuryl fluoride, borax, tartar emetic, or a combination thereof.
[0185] Chordotonal organ TRPV channel modulators: afidopyropen, pymetrozine, pyrifluquinazon, or a combination thereof.
[0186] Mite growth inhibitors: clofentezine, hexythiazox, diflovidazin, etoxazole, or a combination thereof.
[0187] Microbial disruptors of insect midgut membranes: Bacillus thuringiensis, Bacillus sphaericus, and/or the insecticidal proteins they produce, optionally Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Abl, or a combination thereof
[0188] Inhibitors of mitochondrial ATP synthase: diafenthiuron, organotin miticides, optionally azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon, or a combination thereof.
[0189] Uncouplers of oxidative phosphorylation via disruption of the proton gradient: chlorfenapyr, DNOC, sulfluramid, or a combination thereof.
[0190] nAChR channel blockers: nereistoxin analogues bensultap, cartap hydrochloride, thio-cyclam, thiosultap-sodium, or a combination thereof.
[0191] Inhibitors of the chitin biosynthesis type 0: bistrifluron, chlorfluazuron, difluben- zuron, fluey cl oxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, or a combination thereof.
[0192] Inhibitors of the chitin biosynthesis type 1: buprofezin.
[0193] Molting disruptors: Dipteran, cyromazine, or a combination thereof.
[0194] Ecdyson receptor agonists.: methoxyfenozide, tebufenozide, halofenozide, fufeno- zide, chromafenozide, or a combination thereof.
[0195] Octopamin receptor agonists: amitraz.
[0196] Mitochondrial complex III electron transport inhibitors: hydramethylnon, acequinocyl, fluacrypyrim; bifenazate, or a combination thereof. [0197] METI acaricides and insecticides: fenazaquin, fenpyroximate, pyrimidifen, pyrida-ben, tebufenpyrad, tolfenpyrad, rotenone, or a combination thereof.
[0198] Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone, 2-[2- (4-cyanophenyl)-l-[3-(trifluoromethyl)phenyl]^ethylidene]-N-[4-(difluoromethoxy)phenyl]- hydrazinecarboxamide, N-(3-chloro-2-methyl_,phenyl)-2-[(4-chlorophenyl)[4- [methyl(methylsulfonyl)amino]phenyl]_,methylene]-hydrazinecarboxamide, N-[4-chloro-2- [[(l,l-dimethylethyl)amino]carbonyl]-6-methylphenyl]-l-(3-chloro-2-pyridinyl)-3- (fluoromethoxy)-lH-pyrazole-5-carboxamide, 2-[2-(4-cyanophenyl)-l-[3- (trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide. [0199] Inhibitors of the of acetyl CoA carboxylase.: spirodiclofen, spiromesifen, spirotetramat; spiropidion; spirobudifen, 1 l-(4-chl oro-2, 6-dimethylphenyl)-12-hydroxy- 1,4- dioxa-9-azadispiro[4.2.4.2]tetradec-l l-en-10-one, spidoxamat, or a combination thereof.
[0200] Mitochondrial complex IV electron transport inhibitors: aluminium phosphide, calcium phosphide, zinc phosphide, cyanide, or a combination thereof.
[0201] Mitochondrial complex II electron transport inhibitors.: cyenopyrafen, cyflumetofen, cyetpyrafen, pyflubumide, or a combination thereof.
[0202] Ryanodine receptor-modulators: chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, fluchlordiniliprole, (R)-3-chloro-Nl-{2-methyl-4-[l, 2,2,2- tetrafluoro- 1 -(trifluoromethyl)ethyl]phenyl } -N2-( 1 -methyl-2- methylsulfonylethyl)phthalamid, (S)-3 -chloro-N 1 - {2-methyl-4-[ 1 ,2,2,2-tetrafluoro- 1 - (trifluoromethyl)ethyl]phenyl}-N2-(l-methyl-2-methylsulfonylethyl)phthalamide, methyl-2- [3,5-dibromo-2-({[3-bromo-l-(3-chlorpyridin-2-yl)-lH-pyrazol-5-yl]carbonyl}_,ami- no)benzoyl]-l,2-dimethylhydrazine-carboxylate; N-[2-(5-amino-l,3,4-thiadiazol-2-yl)-4- chloro-6-methyl_,phenyl]-3-bromo-l-(3-chloro-2-pyridinyl)-lH-pyrazole-5-carboxamide; 3- chloro-l-(3-chloro-2-pyridinyl)-N-[2,4-dichloro-6-[[(l-cyano-l-methylethyl)ami- no]carbonyl]phenyl]-lH-pyrazole-5-carboxamide; tetrachlorantraniliprole; tetraniliprole; tiorantraniliprole; N-[4-chloro-2-[[(l,l-dimethylethyl)amino]carbonyl]-6-methyl-phenyl]-l- (3-chloro-2-pyridinyl)-3-(fluoromethoxy)-lH-pyrazole-5-carboxamide; cyhalodiamide; N-[2- (5-amino-l,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-l-(3-chloro-2-pyridinyl)- lH-pyrazole-5-carboxamide, or a combination thereof.
[0203] Chordotonal organ Modulators: flonicamid.
[0204] GABA gated chlorine channel allosteric modulators: broflanilide; fluxametamide, isocycloseram, or a combination thereof.
[0205] Calcium-activated potassium channel modulators: acynonapyr. [0206] Mitochondrial complex III electron transport inhibitor QI site: Flometoquin. [0207] Chordotonal organ modulators-undefined target site: Dimpropyridaz.
[0208] Other possible insecticides include: afoxolaner, azadirachtin, amidoflumet, ben- zoximate, bromopropylate, chino_,methionat, cryolite, cyproflanilid, dicloromezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, mivorilaner, modoflaner, piperonyl butoxide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, 1 l-(4-chl oro-2, 6-dimethylphenyl)-12-hydroxy- l,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-l l-en-10-one, 3-(4’-fluoro-2,4-dimethylbiphenyl-3- yl)-4-hydroxy-8-oxa-l-azaspiro[4.5]dec-3-en-2-one, 4-cyano-N-[2-cyano-5-[[[2,6-dibromo- 4-[l,2,2,3,3,3-hexafluoro-l-(trifluoromethyl)propyl]phenyl]amino]carbonyl]phenyl]-2- methyl-benzamide, 4-cyano-3-[(4-cyano-2-methyl-benzoyl)amino]-N-[2,6-dichloro-4- [l,2,2,3,3,3-hexafluoro-l-(trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide, N-[5-[[[2- chloro-6-cyano-4-[l,2,2,3,3,3-hexafluoro-l-(trifluoromethyl)propyl]phenyl]amino]carbonyl]- 2-cyano-phenyl]-4-cyano-2-methyl-benzamide, N-[5-[[[2-bromo-6-chloro-4-[2,2,2-trifluoro- 1 -hydroxy- l-(trifluoromethyl)ethyl]phenyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2- methyl-benzamide, N-[5-[[[2-bromo-6-chloro-4-[l,2,2,3,3,3-hexafluoro-l- (trifluoromethyl)propyl]phenyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2-methyl- benzamide, 4-cyano-N-[2-cyano-5-[[[2,6-dichloro-4-[l,2,2,3,3,3-hexafluoro-l- (trifluoromethyl)propyl]phenyl]amino]carbonyl]phenyl]-2-methyl-benzamide, l-[2-fluoro-4- methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-lH-l,2,4-triazole-5- amine, N-[5-[[[2-bromo-6-chloro-4-[l,2,2,2-tetrafluoro-l-(trifluoromethyl)ethyl]phe- nyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide, 4-cyano-N-[2-cyano-5- [[[2,6-dichloro-4-[l,2,2,2-tetrafluoro-l-(trifluoro- methyl)ethyl]phenyl]amino]carbonyl]phenyl]-2-methyl-benzamide, actives on basis of bacillus firmus (Votivo, 1-1582); fluazaindolizine; 5-[3-[2,6-dichloro-4-(3,3-dichloroallyl- oxy)phenoxy]propoxy]-lH-pyrazole; N-[5-[[2-bromo-6-chloro-4-[l,2,2,3,3,3-hexafluoro-l- (trifluoromethyl)-propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[l,2,2,3,3,3-hexafluoro-l-(trifluoromethyl)- propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; 4-cyano-N-[2-cyano-5-[[2,6-di- chloro-4-[ 1 ,2,2,2-tetrafluoro- 1 -(trifluoromethyl)ethyl]phenyl]carbamoyl]_,phenyl]-2-m ethylbenzamide; N-[5-[[2-bromo-6-chloro-4-[ 1,2,2, 2-tetrafluoro-l -(trifluoromethyl)ethyl]phe- nyl]carba_,moyl]-2-cyano-phenyl]-4-cyano-2-methyl -benzamide; 2-(l,3-dioxan-2-yl)-6-[2-(3- pyridinyl)-5-thiazolyl]-pyridine; 2-[6-[2-(5-fluoro-3-pyridinyl)-5-thiazo_,lyl]-2-pyridinyl]- pyrimidine; 2-[6-[2-(3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; N-methylsuHfonyl-6- [2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; N-methylsulfonyl-6-[2-(3- pyridyl)thiazol-5-yl]pyridine-2-carboxamide; l-[(6-chloro-3-pyridinyl)methyl]-l,2,3,5,6,7- hexahydro-5-methoxy-7-methyl-8-nitro-imidazo[l,2-a]pyridine; l-[(6-chloropyridin-3- yl)methyl]-7-methyl-8-nitro-l,2,3,5,6,7-hexahydroimidazo[l,2-a]pyridin-5-ol; N-(3-chloro-2- methylphenyl)-2-[(4-chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]- hydrazinecarboxamide; 1 -[(6-chl oro-3-pyridinyl)methyl]- 1,2, 3,5,6, 7-hexahy dro-5-methoxy- 7-methyl-8-nitro-imidazo[l,2-a]pyridine; 2-(3-pyridinyl)-N-(2-pyrimidinylmethyl )-2H- indazole-5-carboxamide; tyclopyrazoflor; sarolaner, lotilaner; N-[4-chloro-3-[[(phenyl- methyl)amino]carbonyl]phenyl]- l-methyl-3-(l, 1,2,2, 2-pentafluoroethyl)-4-(trifluoromethyl)- lH-pyrazole-5-carboxamide; N-[4-chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-l- methyl-3-(l,l,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)-lH-pyrazole-5-carboxamide; 2-(3- ethylsulfonyl-2-pyridyl)-3-methyl-6-(tri-fluoromethyl)imidazo[4,5-b]pyridine, 2-[3- ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5- b]pyridine; N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-methyl-5-(l,l,2,2,2- pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide, N-[4-chloro-3-[(l- cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-5-(l, 1,2, 2, 2-pentafluoroethyl)-4-(tri fluoro- methyl)pyrazole-3-carboxamide; benzpyrimoxan; tigolaner; oxazosulfyl; [(2S,3R,4R,5S,6S)- 3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl] N-[4-[l-[4-(trifluoro- methoxy)phenyl]-l,2,4-triazol-3-yl]phenyl]carbamate; [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy- 6-methyl-tetrahydropyran-2-yl] N-[4-[l-[4-(trifluoromethoxy)phenyl]-l,2,4-triazol-3- yl]phenyl]carbamate; [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy- tetrahydropyran-2-yl] N-[4-[l-[4-(l,l,2,2,2-pentafluoroethoxy)phenyl]-l,2,4-triazol-3- yl]phenyl]carbamate; [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl] N- [4-[l-[4-(l,l,2,2,2-pentafluoroethoxy)phenyl]-l,2,4-triazol-3-yl]phenyl]carbamate; (2Z)-3- (2-isopropylphenyl)-2-[(E)-[4-[l-[4-(trifluoromethoxy)phenyl]-l,2,4-triazol-3- yl]phenyl]methylenehydrazono]thiazolidin-4-one, (2Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[l- [4-( 1 , 1 ,2,2,2-pentafluoroethoxy)phenyl]- 1 ,2,4-triazol-3 -yl]phe- nyl]methylenehydrazono]thiazolidin-4-one, (2Z)-3-(2-isopro_,pyl_,phenyl)-2-[(E)-[4-[l-[4- (1,1 ,2,2,2-pentafluoroethoxy)phenyl]- 1 ,2,4-triazol-3 - yl]phenyl]methylenehydrazono]thiazolidin-4-one; 2-(6-chloro-3-ethylsulfonyl-imidazo[l,2- a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(6-bromo-3- ethylsulfonyl-imidazo[l,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5- b]pyridine, 2-(3-ethylsulfonyl-6-iodo-imidazo[l,2-a]pyridin-2-yl)-3-methyl-6-
(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(7-chloro-3-ethylsulfonyl-imidazo[l,2-a]pyridin- 2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(7-chloro-3-ethylsulfonyl- imidazo[l,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(3- ethylsulfonyl-7-iodo-imidazo[l,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5- b]pyridine, 3-ethylsulfonyl-6-iodo-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2- yl]imidazo[l,2-a]pyridine-8-carbonitrile, 2-[3-ethylsulfonyl-8-fluoro-6- (trifluoromethyl)imidazo[l,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5- b]pyridine, 2-[3-ethylsulfonyl-7-(trifluoromethyl)imidazo[l,2-a]pyridin-2-yl]-3-methyl-6- (trifluoromethylsulfinyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-7-(trifluoromethyl)imi- dazo[l,2-a]pyri din-2 -yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyri dine, 2-(6-bromo-3- ethylsulfonyl-imidazo[l,2-a]pyridin-2-yl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine; N-[[2- fluoro-4-[(2S,3S)-2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidin-l- yl]phenyl]methyl]cyclopropanecarboxamide; 2-[2-fluoro-4-methyl-5-(2,2,2- trifluoroethylsulfinyl)phenyl]imino-3-(2,2,2-trifluoroethyl)thiazolidin-4-one; flupentiofenox, N-[3-chloro-l-(3-pyridyl)pyrazol-4-yl]-2-methylsulfonyl-propanamide, cyclobutrifluram; N- [4-chloro-3-[(l-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-4-methylsulfonyl-5- ( 1,1, 2, 2, 2-pentafluoroethyl)pyrazole-3 -carboxamide, cyproflanilide, nicofluprole; 1,4- dimethyl-2-[2-(pyridin-3-yl)-2h-indazol-5-yl]-l, 2, 4-triazolidine-3, 5-dione, 2-[2-fluoro-4- methyl-5-(2,2,2-trifluoroethylsulfanyl)phenyl]imino-3-(2,2,2-trifluoroethyl)thiazolidin-4-one, indazapyroxamet, N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylsulfonyl- propanamide, N-cyclopropyl-5-[(5S)-5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)- 4H-isoxazol-3-yl]isoquinoline-8-carboxamide, 5-[(5S)-5-(3,5-dichloro-4-fluoro-phenyl)-5- (trifluoromethyl)-4H-isoxazol-3-yl]-N-(pyrimidin-2-ylmethyl)isoquinoline-8-carboxamide, N-[l-(2,6-difluorophenyl)pyrazol-3-yl]-2-(trifluoromethyl)benzamide, 5-((lR,3R)-3-(3,5- Bis(trifluoromethyl)phenyl)-2,2-dichlorocyclopropane-l-carboxamido)-2-chloro-N-(3-(2,2- difluoroacetamido)-2,4-difluorophenyl)benzamide, l-[6-(2,2-difluoro-7-methyl- [l,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile, 6- (5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro-7-methyl-[l,3]dioxolo[4,5- f]benzimidazole, or a combination thereof.
[0209] The commercially available compounds listed above may be found in The Pesticide Manual, 18th Edition, C. MacBean, British Crop Protection Council (2018), or bcpcdata.com/pesticide-manual.html; alanwood.net/pesticides.
[0210] The insecticides and pesticides listed above can be found in patent documents CN103814937; W02013/003977, W02007/101369, WO2018/177970, CN10171577, CN102126994, W02007/101540, W02007/043677, WO2011/085575, WO2008/134969, W02012/034403, W02006/089633, W02008/067911, W02006/043635, W02009/124707, WO20 13/050317, WO2010/060379, WO2010/127926, WO2010/006713, W02012/000896, W02007/101369, WO2012/143317, W02015/038503, EP2910126, W02015/059039, W02015/190316, WO2012/126766, W02009/102736, WO2013/116053, WO2018/052136, WO2015150252, W02020055955, WO2021158455, W02013092350, WO201811111, EP3608311, WO2019236274, W02013092350, WO 2018052136, W02009102736, WO2016174049, WO2012126766, CN106554335, WO2017054524, CN105153113, W02022072650; WO2018071327, W02022101502, WO2012158396, W02007079162, and W02020013147.
[0211] The insecticides can further comprise biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, ( ,Z)-7,9- dodecadien-l-yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)- 7,11,13 -hexadecatri enal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cisjasmone, 2-methyl 1-butanol, methyl eugenol, methyl jasmonate, (E,Z)-2, 13 -octadecadi en-1- ol, (/'/Z)-2, l 3 -octadecadi en- l -ol acetate, (/yZ)-3, l 3 -octadecadi en- l -ol, (A)-l-octen-3-ol, pentatermanone, (E,Z,Z)-3,8,l l-tetradecatrienyl acetate, (Z,£)-9,12-tetradecadien-l-yl acetate, (Z)-7-tetradecen-2-one, (Z)-9-tetradecen-l-yl acetate, (Z)-l l-tetradecenal, (Z)-l 1- tetradecen-l-ol, extract of Chenopodium ambrosiode , Neem oil, Quillay extract, or a combination thereof.
[0212] Any one or a combination of any of the insecticides can be selected.
[0213] The insecticide can be selected from the group consisting of acephate, cypermethrin, cyhalothrin, bifenthrin, imidacloprid, acetamiprid, dinotefuran, thiacloprid, chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, broflanilide, isocycloseram, or combinations thereof.
[0214] The insecticide can be present in compositions in a range from 0.001 to 10,000 ppm, preferably from 0.1 to 2000 ppm, most preferably from 1 to 1000 ppm.
[0215] The insecticide can comprise a combination of any of the insecticides listed herein, for example, the insecticide can comprise a combination of a AChE inhibitor, GABA-gated chloride channel antagonist, Sodium channel modulator, nAChR agonist, nicotinic acetylcholine receptor allosteric activator, chloride channel activator, juvenile hormone mimic, chordontonal organ TRPV channel modulator, mite growth inhibitor, inhibitor of mitochondrial ATP synthase, uncoupler of oxidative phosphorylation, inhibitor of the chitin biosynthesis type 0, ecdyson receptor agonist, METI acaricide and insecticide, voltagedependent sodium channel blocker, inhibitor of the acetyl CoA carboxylase, mitochondrial complex II electron transport inhibitor, ryanodine receptor-modulator, chordontonal organ modulator, GABA gated chlorine channel allosteric modulator, calcium-activated potassium channel modulator, mitochondrial complex III electron transport inhibitor QI site, chordontonal organ modulators-undefined target site, a insecticide of unknown mode of action, and a biochemical pesticide.
[0216] The insecticide can be acephate, cypermethrin, cyhalothrin, bifenthrin, imidacloprid, acetamiprid, dinotefuran, thiacloprid, chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, broflanilide, isocycloseram, or a combination thereof.
[0217] Cyclodextrins
[0218] The insecticide can be associated with a cyclodextrin molecular basket. For example, the insecticide can be loaded within a cyclodextrin molecular basket. The insecticide forms an inclusion complex with the cyclodextrin. Therefore, the insecticide can be indirectly linked to the gamma-cyclodextrin via the cyclodextrin molecular basket (optionally, that is functionalized with the gamma-cyclodextrin; or that is linked to a nanoparticle functionalized with the gamma-cyclodextrin). The loading of the insecticide in the cyclodextrin molecular basket allows for a controlled release of the insecticide.
[0219] The pesticide, optionally an insecticide, can be associated with a cyclodextrin molecular basket. For example, the insecticide can be loaded within a cyclodextrin molecular basket. The insecticide forms an inclusion complex with the cyclodextrin. Therefore, the pesticide, optionally an insecticide, can be indirectly linked to the gamma-cyclodextrin via the cyclodextrin molecular basket (optionally, that is functionalized with the gamma-cyclodextrin; or that is linked to a nanoparticle functionalized with the gamma-cyclodextrin). The loading of the pesticide, optionally an insecticide, in the cyclodextrin molecular basket allows for a controlled release of the pesticide, optionally an insecticide.
[0220] The cyclodextrin forming the molecular basket can comprise an alpha-cyclodextrin, beta- cyclodextrin, gamma-cyclodextrin, or a combination thereof. The cyclodextrin can be a gamma-cyclodextrin. The insecticide can form a complex with the molecular basket (optionally, loaded into a molecular basket). The cyclodextrin molecular basket can be linked either directly or indirectly to a nanoparticle.
[0221] Conjugates
[0222] A conjugate comprising a gamma-cyclodextrin linked to a cargo, wherein the conjugate is capable of being delivered to a plant (, optionally, to a desired site within the plant, e.g., a leaf), and wherein the cargo is an agent that is capable of producing a desired effect in the plant following delivery of the conjugate to the plant.
[0223] A conjugate comprising a gamma-cyclodextrin or a gamma-cyclodextrin linked to a cargo that is an insecticide. A conjugate as described herein comprises a mixture of cyclodextrins.
[0224] A conjugate comprising a gamma-cyclodextrin or a gamma-cyclodextrin linked to a cargo that is a pesticide, optionally an insecticide. A conjugate as described herein comprises a mixture of cyclodextrins.
[0225] The conjugate can comprise a nanoparticle and a cyclodextrin molecular basket. For example, a nanoparticle (NP) and a cyclodextrin molecular basket conjugate can serve as delivery vehicle for an insecticide. For example, insecticide can be carried within the cyclodextrin molecular basket and can be released on the surface of a plant. In particular, when linked with a gamma-cyclodextrin, a higher proportion of the conjugate described herein can be introduced to a plant surface and reach a target site of action (, optionally, leaf surface), improving available insecticide. When linked with a gamma-cyclodextrin, a higher proportion of the conjugate can be applied to a plant as compared to a control delivery vehicle without the gamma-cyclodextrin.
[0226] The conjugate can have an average size of between about 1 nm and 10 nm. For example, the conjugate can have an average size of between about 3 and 6 nm, 4 and 8 nm, 5 and 9 nm. The conjugate can have an average size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm. [0227] The conjugate diameter is a hydrodynamic diameter (, optionally, determined by dynamic light scattering). The conjugate diameter is determined by electron microscopy. The nanoparticle or a conjugate diameter can be determined by atomic force microscopy (AFM) or transmission electron microscopy (TEM).
[0228] Compositions
[0229] A composition can comprise a conjugate described herein.
[0230] A conjugate as described herein can be formulated into a suitable dosage form for plant application/introduction.
[0231] Common agrochemical formulations include but are not limited to liquid and solid formulations. Exemplary formulations include gel, aqueous or oil-based solutions, dispersions, suspensions or emulsions. U.S. Patent Nos 5,139,152; 6,403,529; 6,878,674; 7,094,831; 7,109,267 and 9,706,771.
[0232] The conjugate can be formulated in a liquid formulation, which can be administered or sprayed onto a plant using, optionally, ground/aerial spraying. [0233] The conjugate can be formulated in pellet or tablet formulations. Such formulations can be capable of rapid break-up in water using minimal or no agitation while providing fine dispersions of the active ingredient.
[0234] The composition can comprise agriculturally acceptable additives or excipients. Suitable additives or excipients include but are not limited to organic solvents, solubilizers, emulsifiers, surfactants, dispersants, preservatives, colorants, fillers, diluents, binders, glidants, lubricants, disintegrants, anti-adherents, sorbents, coatings, wetting agents, penetrants, vehicles, and combinations thereof. Additives, excipients and agrochemical formulations are described in U.S. Patent No. 6,602,823.
[0235] A composition described herein can comprise a surfactant. The surfactant can be a non-ionic surfactant (optionally, organosilicone surfactant Silwet, e.g., Silwet L-77). The surfactant can improve the spreading of the composition (optionally, liquid composition) on the leaf surface, and/or can facilitate the uptake of a conjugate described herein across the leaf lamina. The surfactant can facilitate uptake into leaf stomatai pores and/or increase permeability in the leaf epidermal layer, optionally, through partial removal of the cuticular layer. The composition can be in a powder dosage form.
[0236] The composition described herein can be in a lyophilized form and reconstituted into liquid form before use.
[0237] Linker
[0238] A linker can link a nanoparticle to a cyclodextrin molecular basket. The linker can be 4-caryboxylphenyl boronic acid (CBPA). The linker can be 4-aminophenylboronic acid.
[0239] Methods
[0240] A method of treating a plant (optionally, comprising a pest) in need thereof can comprise contacting the plant with an effective amount of a conjugate as described herein. For example, a method of treating a plant in need thereof, wherein the plant has a phloem pathogen or a root pathogen, the method comprising contacting the plant with an effective amount of a conjugate as described herein.
[0241] Contacting the plant can comprise contacting a leaf of the plant. Contacting the plant can comprise contacting the top surface of a leaf of the plant.
[0242] The delivered conjugate is more efficiently delivered into the stem and/or root of the plant as compared to a control material that is not linked with the gamma-cyclodextrin.
[0243] The plant can be a fruit, vegetable, field crop, or a combination thereof.
[0244] The field crop can be what, oat, com soybean, rice, barley, or a combination thereof. [0245] The vegetable crop can be lettuce, broccoli, carrot, spinach, pepper, or a combination thereof.
[0246] The fruit crop can be apple, orange, pear, grape, peach, or combination thereof. [0247] The plant can be a nut tree, optionally an almond, walnut, pecan tree, or combination thereof.
[0248] The plant can be cotton, flax, or a combination thereof.
[0249] The plant can be blackberry, cabbage, com, tomato, eggplant, bean, soybean, or a combination thereof. The plant can be a tree, optionally apple, peach, pecan, cherry, or a combination thereof. The plant can be a columbine, snapdragon, sunflower, or a combination thereof.
[0250] The compounds of the disclosure are especially suitable for efficiently combating animal pests, optionally arthropods, gastropods, nematodes, or combinations thereof, including, but not limited to:
[0251] Insects from the order of Lepidoptera, optionally Achroia grisella, Acleris spp., optionally A. fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp., optionally A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp., optionally A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A. subterranea; Alabama argillacea, Aleurodicus dispersus, Alsophila pometaria, Ampelophaga rubiginosa, Amyelois transitella, Anacampsis sarcitella, Anagasta kuehniella, Anarsia lineatella, Anisota senatoria, Antheraea pernyi, Anticarsia spp., optionally A. gemmatalis; Apamea spp., Aproaerema modicella, Archips spp., optionally A. argyrospila, A. fuscocupreanus, A. rosana, A. xyloseanus; Argyresthia conjugella, Argyroploce spp., Argyrotaenia spp., optionally A. velutinana; Athetis mindara, Austroasca verdigrises, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busse ola spp., Cacoecia spp., optionally C. murinana, C. podana; Cactoblastis cactorum, Cadra cautella, Calingo braziliensis, Caloptilis theivora, Capua reticulana, Carposina spp., optionally C. niponensis, C. sasakii; C ephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp., optionally C. Indicus, C. suppressalis, C. partellus; Choreutis pariana, Choristoneura spp., optionally C. conflictana, C. fumiferana, C. longicellana, C. murinana, C. occidentalis, C. rosaceana; Chrysodeixis (=Pseudoplusia) spp., optionally C. er iosoma, C. includens; Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Cochylis hospes, Coleophora spp., Colias eury theme, Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Corcyra cephalonica, Crambus caliginosellus, Crambus teterrellus, Crocidosema (=Epinotia) aporema, Cydalima (=Diaphania) perspectalis, Cydia (=Carpocapsa) spp., optionally C. pomonella, C. latiferreana; Dalaca noctuides, Datana integerrima, Dasychira pinicola, Dendrolimus spp., optionally D. pini, D. spectabilis, D. sibir icus; Desmia funeralis, Diaphania spp., optionally D. nitidalis, D. hyalinata; Diatraea grandiosella, Diatraea saccharalis, Diphthera f estiva, Earias spp., optionally E. insulana, E. vittella; Ecdytolopha aurantianu, Egira (=Xylomyges) curialis, Elasmopalpus lignosellus, Eldana sac char ina, Endopiza viteana, Enno-mos sub signaria, Eoreuma loftini, Ephestia spp., optionally E. cautella, E. elutella, E. kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp., optionally F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp., optionally G. funebrana, G. molesta, G. inopinata; Halysidota spp., Harrisina americana, Hedylepta spp., Helicoverpa spp., optionally H. armigera (=Heliothis armigera), H. zea (=Heliothis zea) ; Heliothis spp., optionally H. assulta, H. subflexa, H. virescens; Hellula spp., optionally H. undalis, H. rogatalis; Helocoverpa gelotopoeon, Hemileuca oliviae, Herpetogramma licarsisalis, Hibernia defoliaria, Hofinannophila pseudospretella, Homoeosoma electellum, Homona magna nima, Hypena scabra, Hyphantria cunea, Hyponomeuta padella, Hypono meula malinellus, Kakivoria flavofasciata, Keiferia lycopersicella, Lambdina fiscellaria, Lambdina fiscellaria lugubrosa, Lamprosema indicata, Laspeyresia molesta, Leguminivora glycinivorella, Lerodea eufala, Leucinodes orbonalis, Leucoma salicis, Leucopter a spp., optionally L. coffeella, L. scitella; Leuminivora lycinivorella, Lithocolletis blancardella, Lithophane antennata, Llattia octo (=Amyna axis), Lobesia botrana, Lophocampa spp., Loxagrotis albicosta, Loxostege spp., optionally L. sticticalis, L. cereralis; Lymantria spp., optionally L. dispar, L. monacha; Lyonetia clerkella, Lyonetia prunifoliella, Malacosoma spp., optionally M. americanum, M. californicum, M. constrictum, M. neu-stria; Mamestra spp., optionally M. brassicae, M. configurata; Mamstra brassicae, Manduca spp., optionally M. quinquemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mods spp., optionally M. lapites, M. repanda; Mods latipes, Monochroa fragariae, Mythimna separata, Nemapogon cloacella, Neoleucinodes elegantalis, Nepytia spp., Nymphula spp., Oiketicus spp., Omiodes indicata, Omphisa anastomosalis, Operophtera brumata, Orgyia pseudotsugata, Oria spp., Orthaga thyrisalis, Ostrinia spp., optionally O. nubilalis; Oulema oryzae, Paleacrita vernata, Panolis flammea, Parnara spp., Papaipema nebris, Papilio cresphontes, Paramyelois transitella, Paranthrene regalis, Paysandisia archon, Pectinophora spp., optionally P. gossypiella; Peridroma saucia, Perileucopter a spp., optionally P. coffeella; Phalera bucephala, Phryganidia californica, Phthorimaea spp., optionally P. operculella; Phyllocnistis citrella, Phyllonorycter spp., optionally P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp., optionally P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathypena scabra, Platynota spp., optionally P. flavedana, P. idaeusalis, P. stultana; Platyptilia carduidactyla, Plebejus argus, Plodia interpunctella, Plusia spp, Plutella maculipennis, Plutella xylostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus lepigone, Pseudaletia spp., optionally P. sequax, P. unipuncta; Pyrausta nubilalis, Rachiplusia nu, Richia albicosta, Rhizobius ventralis, Rhyacioniafrustrana, Sabulodes aegrotata, Schizura concinna, Schoenobius spp., Schreckensteinia festaliella, Scirpophaga spp., optionally S. incertulas, S. innotata; Scotia segetum, Sesamia spp., optionally S. infer ens, Seudyra subjlava, Sitotroga cerealella, Sparganothis pilleriana, Spilonota lechriaspis, S. ocellina, Spodoptera (=Lamphygma) spp., optionally S. cosmoides, S. eridania, S. exigua, S. frugiperda, S. latisfascia, S. littoralis, S. litura, S. omithogalli; Stigmella spp., Stomopteryx subsecivella, Strymon bazochii, Sy lepta der ogata, Synanthedon spp., optionally S. exitiosa, Tecia solanivora, Telehin licus, Thaumatopoea pityocampa, Thaumatotibia (=Cryptophlebia) leucotreta, Thaumetopoea pityocampa, Theda spp., Theresimima ampelophaga, Thyrinteina spp, Tildenia inconspicuella, Tinea spp., optionally T. cloacella, T. pellionella; Tineola bisselliella, Tortrix spp., optionally T. viridana; Trichophaga tapetzella, Trichoplusia spp., optionally T. ni; Tuta (=Scrobipalpula) absoluta, Udea spp., optionally U. rubigalis, U. rubigalis;
Virachola spp., Yponomeuta padella, and Zeiraphera canadensis.
[0252] Insects from the order of Coleoptera, optionally Acalymma vittatum, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus spp., optionally A. anxius, A. planipennis, A. sinuatus; Agriotes spp., optionally A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimallus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala corpulenta, Anomala rufocuprea, Anoplophora spp., optionally A. glabripennis; Anthonomus spp., optionally A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogonia spp., Athous haemorrhoidalis, Atomaria spp., optionally A. linearis; Attagenus spp., Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp., optionally B. lentis, B. pisorum, B. rufimanus; Byctiscus betulae, Callidiellum rufipenne, Callopistria jloridensis, Callosobruchus chinensis, Cameraria ohridella, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp., optionally C. assimilis, C. napi; Chaetocnema tibialis, Cleonus mendicus, Conoderus spp., optionally C. vespertinus; Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestesferrugineus, Cryptorhynchus lapathi, Ctenicera spp., optionally C. destructor; Curculio spp., Cylindrocopturus spp., Cyclocephala spp., Dac-tylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp., optionally D. undecimpunctata, D. speciosa, D. longicornis, D. semipunctata, D. virgifera; Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp., optionally E. varivestis, E. vigintioctomaculata; Epitrix spp., optionally E. hirtipennis, E. similar is; Eutheola humilis, Eutinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hyper a spp., optionally H. brunneipennis, H. postica; Hypomeces squamosus, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lerna spp., optionally L. bilineata, L. melanopus; Leptinotarsa spp., optionally L. decemlineata; Leptispa pygmaea, Limonius calif ornicus, Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp., optionally L. bruneus; Liogenys fuscus, Macrodactylus spp., optionally M. subspinosus; Maladera matrida, Megaplatypus mutates, Megascelis spp., Melanotus communis, Meligethes spp., optionally M. aeneus; Melolontha spp., optionally M. hippocastani, M. melolontha; Metamasius hemipterus, Microtheca spp., Migdolus spp., optionally M. fryanus, Monochamus spp., optionally M. alternatus; Naupactus xanthographus, Niptus hololeucus, Oberia brevis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Otiorrhynchus sulcatus, Oulema melanopus, Oulema oryzae, Oxycetonia jucunda, Phaedon spp., optionally P. brassicae, P. cochleariae; Phoracantha recurva, Phyllobius pyri, Phyllopertha horticola, Phyllophaga spp., optionally P. helleri; Phyllotreta spp., optionally P. chrysocephala, P. nemorum, P. striolata, P. vittula; Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psacothea hilar is, Psylliodes chrysocephala, Prostephanus truncates, Psylliodes spp., Ptinus spp., Pulga saltona, Rhizopertha dominica, Rhynchophorus spp., optionally R. billineatus, R. ferrugineus, R. palmarum, R. phoenicis, R. vulneratus; Saperda Candida, Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp., optionally S. granaria, S. oryzae, S. zeamais; Sphenophorus spp., optionally S. levis; Stegobium paniceum, Sterne chus spp., optionally S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp., optionally T. castaneum; Trogoderma spp., Ty chius spp., Xylotrechus spp., optionally X. pyrrhoderus; and, Zabrus spp., optionally Z. tenebrioides.
[0253] Insects from the order of Diptera, optionally Aedes spp., optionally A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp., optionally A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bactrocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chrysomyia spp., optionally C. bezziana, C. hominivorax, C. macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp., optionally C. hominivorax; Contarinia spp., optionally C. sorghicola; Cordylobia anthropophaga, Culex spp., optionally C. nigripalpus, C. pipiens, C. quinquefasciatus, C. tarsalis, C. tritaeniorhynchus; Culicoides furens, Culiseta inornata, Culiseta melanura, Cuter ebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Dasineura oxycoccana, Delia spp., optionally D. antique, D. coarctata, D. platura, D. radicum; Dermatobia hominis, Drosophila spp., optionally D. suzukii, Fannia spp., optionally F. canicularis; Gastraphilus spp., optionally G. intestinalis; Geomyza tipunctata, Glossina spp., optionally G.fuscipes, G. morsitans, G. palpalis, G. tachinoides; Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp., optionally H. platura;
Hypoderma spp., optionally H. lineata; Hyppobosca spp., Hydrellia philippina, Leptoconops torr ens, Liriomyza spp., optionally L. sativae, L. trifolii; Lucilia spp., optionally L. caprina,
L. cuprina, L. sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp., optionally
M. destructor; Musca spp., optionally M. autumnalis, M. domestica; Muscina stabulans, Oestrus spp., optionally O. ovis; Opomyza florum, Oscinella spp., optionally O.frit;
Orseolia oryzae, Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp., optionally P. antiqua, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis spp., optionally R. cerasi, R. cingulate, R. indiffer ens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp., optionally S. haemorrhoidalis; Simulium vittatum, Sitodiplosis mosellana, Stomoxys spp., optionally S. calcitrans; Tabanus spp., optionally T. atratus, T. bovinus, T. lineola, T. similis; Tannia spp., Thecodiplo-sis japonensis, Tipula oleracea, Tipula paludosa, and Wohlfahrtia spp.
[0254] Insects from the order of Thysanoptera, optionally, Baliothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp., optionally F.fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kelly anus, Rhipiphorothrips cruentatus, Scirtothrips spp., optionally S. citri, S. dorsalis, S. perseae; Stenchaetothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp., optionally T. imagines, T. hawaiiensis, T. oryzae, T. palmi, T. parvispinus, T. tabaci.
[0255] Insects from the order of Hemiptera, optionally, Acizzia jamatonica, Acrosternum spp., optionally A. hilare; Acyrthosipon spp., optionally A. onobrychis, A. pisum; Adelges laricis, Adelges tsugae, Adelphocoris spp., optionally A. rapidus, A. superbus; Aeneolamia spp., Agonoscena spp., Aulacorthum solani, Aleurocanthus woglumi, Aleurodes spp., Aleurodicus disperses, Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp., optionally A. craccivora, A.fabae, A.forbesi, A. gossypii, A. grossulariae, A. maidiradicis, A. pomi, A. sambuci, A. schneideri, A. spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacaspis yasumatsui, Aulacorthum solani, Bactericera cocker elli (Paratrioza cocker elli), Bemisia spp., optionally B. argentifolii, B. tabaci (Aleurodes tabaci); Blissus spp., optionally B. leucopterus;
Brachycaudus spp., optionally B. cardui, B. helichrysi, B. persicae, B. prunicola; Brachycolus spp., Brachycorynella as-paragi, Brevicoryne brassicae, Cacopsylla spp., optionally C. fulguralis, C. pyricola (Psyllapiri); Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horni, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Cimex spp., optionally C. hemipterus, C. lectularius; Coccomytilus halli, Coccus spp., optionally C. hesperidum, C. pseudomagnoliarum; Corythucha arcuata, Creontiades dilutus, Cryptomyzus ribis, Chrysomphalus aonidum, Cryptomyzus ribis, Ctenarytaina spatulata, Cyrtopeltis notatus, Dalbulus spp., Dasynus piperis, Dialeurodes spp., optionally D. citrifolii; Dalbulus maidis, Diaphorina spp., optionally D. citri; Diaspis spp., optionally D. bromeliae; Dichelops furcatus, Diconocoris hewetti, Doralis spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp., optionally D. plantaginea, D. pyri, D. radicola;
Dysaulacorthum pseudosolani, Dysdercus spp., optionally D. cingulatus, D. intermedins; Dysmicoccus spp., Edessa spp., Geocoris spp., Empoasca spp., optionally E.fabae, E. solana; Epidiaspis leper ii, Er iosoma spp., optionally E. lanigerum, E. pyricola;
Erythroneura spp., Eurygaster spp., optionally E. integriceps; Euscelis bilobatus, Euschistus spp., optionally E. her os, E. impictiventris, E. servus; Fiorinia theae, Geococcus cofifeae, Glycaspis brimblecombei, Halyomorpha spp., optionally H. halys; Heliopeltis spp., Homalodisca vitripennis (=H. coagulata), Horcias nobilellus, Hyalopterus pruni, Hyper omy zus lactucae, Icerya spp., optionally I. purchase; Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp., optionally L. ulmi; Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp., optionally L. hesperus, L. lineolaris, L. praten-sis; Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus, Macrosiphum spp., optionally M. rosae, M. avenae, M. euphorbiae; Macrosteles quadrilineatus, Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Melanocallis (=Tinocallis) caryaefoliae, Metcafiella spp., Metopolophium dirhodum, Monellia costalis, Mo-nelliopsis pecanis, Myzocallis coryli, Murgantia spp., My zus spp., optionally M. ascalonicus, M. cerasi, M. nicotianae, M. persicae, M. varians; Nasonovia ribisnigri, Neotoxoptera formosana, Neomegalotomus spp, Nephotettix spp., optionally N. malayanus, N. nigropictus, N. parvus, N. virescens; Ne zara spp., optionally N. viridula; Nilaparvata lugens, Nysius huttoni, Oebalus spp., optionally 0. pug nax; Oncometopia spp., Orthezia praelonga, Oxycaraenus hyalinipennis, Parabemisia myricae, Parlatoria spp., Parthenolecanium spp., optionally P. corni, P. persicae; Pemphigus spp., optionally P. bursarius, P. populivenae; Peregrinus maidis, Perkinsiella saccharicida, Phenacoccus spp., optionally P. aceris, P. gossypii; Phloeomyzus passer inii, Phorodon humuli, Phylloxera spp., optionally P. devastatrix, Piesma quadrata, Piezodorus spp., optionally P. guildinii; Pinnaspis aspidistrae, Pianococcus spp., optionally P. citri, P. ficus; Prosapia bicincta, Protopulvinaria pyriformis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp., optionally P. comstocki; Psy Ila spp., optionally P. mali; Pteromalus spp., Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., optionally Q. perniciosus; Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp., optionally R. pseudobrassicas, R. inser turn, R. maidis, R. padi; Sagatodes spp., Sahlbergella singula ris, Saissetia spp., Sappaphis mala, Sappaphis mali, Scaptocoris spp., Scaphoides titanus, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insular is, Spissistilus festinus (=Stictocephala festina), Stephanitis nashi, Stephanitis pyrioides, Stephanitis takeyai, Tenalaphara malayensis, Tetraleur odes per seae, Ther ioaphis maculate, Thyanta spp., optionally T. accerra, T. perditor; Tibraca spp., Tomaspis spp., Toxoptera spp., optionally T. aurantii; Trialeur odes spp., optionally T. abutilonea, T. ricini, T. vapor ariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp., optionally U ci tri, U yanonensis; and Viteus vitifolii.
[0256] Insects from the order Hymenoptera, optionally Acanthomyops interjectus, Athalia rosae, Atta spp., optionally A. capiguara, A. cephalotes, A. cephalotes, A. laevigata, A. robusta, A. sexdens, A. texana, Bombus spp., Brachymyrmex spp., Camponotus spp., optionally C. floridanus, C. pennsylvanicus, C. modoc; Cardiocondyla nuda, Chalibion sp, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Dorymyrmex spp., Dryocosmus kuriphilus, Formica spp., Hoplocampa spp., optionally H. minuta, H. testudinea; Iridomyrmex humilis, Lasius spp., optionally L. niger, Linepithema humile, Liometopum spp., Leptocybe invasa, Monomorium spp., optionally M. pharaonis, Monomorium, Nylandria fulva, Pachycondyla chinensis, Paratrechina longicornis, Paravespula spp., optionally P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp., optionally P. megacephala; Pogonomyrmex spp., optionally P. barbatus, P. calif or nicus, Polistes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sir ex cyaneus, Solenopsis spp., optionally S. geminata, S.invicta, S. molesta, S. richteri, S. xyloni, Sphecius speciosus, Sphex spp., Tapinoma spp., optionally T. melanocephalum, T. sessile; Tetramorium spp., optionally T. caespitum, T. bicarinatum, Vespa spp., optionally V. crabro; Vespula spp., optionally V. squamosal; Wasmannia auropunctata, Xylocopa sp.
[0257] Insects from the order Orthoptera, optionally Acheta domesticus, Calliptamus italicus, Chortoicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp., optionally G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp., optionally L. migrator ia, L. pardalina; Melanoplus spp., optionally M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M. spretus; Nomadacris septemfasciata, Oedaleus senegalensis, Scapteriscus spp., Schistocerca spp., optionally S. americana, S. gregaria, Stemopelmatus spp., Tachycines asynamorus, and Zonozerus variegatus.
[0258] Pests from the Class Arachnida, optionally Acari, optionally of the families Argasidae, Ixodidae and Sar-coptidae, optionally Amblyomma spp. (optionally A. americanum, A. variegatum, A. maculatum), Ar gas spp., optionally A. per sicu), Boophilus spp., optionally B. annulatus, B. decoloratus, B. microplus, Dermacentor spp., optionally D.silvarum, D. andersoni, D. variabilis, Hyalomma spp., optionally H. truncatum, Ixodes spp., optionally I. ricinus, I. rubicundus, I. scapular is, I. holocyclus, I. pacificus, Rhipicephalus sanguineus, Ornithodorus spp., optionally O. moubata, O. hermsi, O. turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp., optionally P. ovis, Rhipicephalus spp., optionally R. sanguineus, R. appendiculatus, Rhipicephalus evertsi, Rhizogly phus spp., Sarcoptes spp., optionally S. Scabiei; and Family Eriophyidae including Aceria spp., optionally A. sheldoni, A. anthocoptes, Acallitus spp., Aculops spp., optionally A. lycopersici, A. pelekassi; Aculus spp., optionally A. schlechtendali; Colomerus vitis, Epitrimerus pyri, Phyllocoptruta oleivora; Eriophytes ribis and Eriophyes spp., optionally Eriophyes sheldoni; Family Tarsonemidae including Hemitar sonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Stenotarsonemus spp. Steneotarsonemus spinki; Family Tenuipalpidae including Brevipalpus spp., optionally B. phoenicis; Family Tetranychidae including Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Petrobia latens, Tetranychus spp., optionally T. cinnabarinus, T. evansi, T. kanzawai, T, pacificus, T. phaseulus, T. telarius and T. urticae; Bryobia praetiosa; Panonychus spp., optionally P. ulmi, P. citri; Metatetranychus spp. and Oligonychus spp., optionally O. pratensis, O. perseae, Vasates lycopersici; Raoiella indica, Family Carpoglyphidae including Carpoglyphus spp.; Penthaleidae spp., optionally Halotydeus destructor; Family Demodi cidae with species, optionally Demodex spp.; Family Trombicidea including Trombicula spp.; Family Macronyssidae including Ornothonyssus spp.; Family Pyemotidae including Pyemotes tritici; Tyrophagus putrescentiae; Family Acaridae including Acarus siro; Family Araneida including Latrodectus mactans, Tegenaria agrestis, Chi-racanthium sp, Lycosa sp Achaearanea tepidariorum and Loxosceles reclusa. [0259] Pests from the Phylum Nematoda, optionally plant parasitic nematodes, optionally root-knot nematodes, Meloidogyne spp., optionally M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp., optionally G. rostochiensis; Heterodera spp., optionally H. avenae, H. glycines, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp.; Stem and foliar nematodes, Aphelenchoides spp., optionally A. besseyi; Sting nematodes, Belonolaimus spp., optionally B. longicaudatus; Pine nematodes, Bursaphelenchus spp., optionally B. lignicolus, B. xylophilus; Ring nematodes, Criconema spp., Criconemella spp., optionally C. xenoplax and C. ornata; and, Criconemoides spp., optionally Criconemoides informis; Mesocriconema spp. Stem and bulb nematodes, Ditylenchus spp., optionally D. destructor, D. dipsaci; Awl nematodes, Dolichodorus spp.; Spiral nematodes, Heliocotylenchus multicinctus; Sheath and sheathoid nematodes, Hemicycliophora spp. and Hemicriconemoides spp. ; Hirshmanniella spp. ; Lance nematodes, Hoploaimus spp.; False rootknot nematodes, Nacobbus spp.; Needle nematodes, Longidorus spp., optionally L. elongatus; Lesion nematodes, Pratylenchus spp., optionally P. brachyurus, P. neglectus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nema-todes, Radopholus spp., optionally R. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylenchus spp., optionally R. robustus, R. reniformis: Sculellonema spp. Stubby-root nematode, Trichodorus spp., optionally T. obtusus, T. primitivus; Paratrichodorus spp., optionally P. minor,' Stunt nematodes, Tylenchorhynchus spp., optionally T. claytoni, T. dubius; Citrus nematodes, Tylenchulus spp., optionally T. semipenetrans; Dagger nematodes, Xiphinema spp., ' and other plant parasitic nematode species.
[0260] Insects from the order Blattodea, optionally Macrotermes spp., optionally M. natalensis; Cornitermes cu-mulans, Procornitermes spp., Globitermes sulfur eus, Neocapritermes spp., optionally N. opacus, N. parvus; Odontotermes spp., Nasutitermes spp., optionally N. corniger; Coptotermes spp., optionally C. for-mosanus, C. gestroi, C. acinaciformis; Re ticulitermes spp., optionally R. hesperus, R. tibialis, R. speratus, R. jlavipes, R. grassei, R. lucifugus, R. virginicus; Heterotermes spp., optionally H. aureus, H. longiceps, H. tenuis; Cryptotermes spp., optionally C. brevis, C. cavifrons; Incisitermes spp., optionally I. minor, I. snyderi; Marginitermes hubbardi, Kalotermes jlavicollis, Neotermes spp., optionally N. cas-taneus, Zootermopsis spp., optionally Z. angusticollis, Z. nevadensis, Mastotermes spp., optionally M. dar-winiensis; Blatta spp., optionally B. oriental is, B. lateralis; Blattella spp., optionally B. asahinae, B. germanica; Rhyparobia maderae, Panchlora nivea, Periplaneta spp., optionally P. americana, P. australasiae, P. brunnea, P. fuliginosa, P. japonica; Supella longipalpa, Parcoblatta pennsylvanica, Eurycotis jloridana, Pycnoscelus surinamensis.
[0261] Insects from the order Siphonoptera, optionally Cediopsylla simples, Ceratophyllus spp., Ctenoce-phalides spp., optionally C.felis, C. canis, Xenopsylla cheopis, Pulex irritans, Trichodectes canis, Tunga penetrans, and Nosopsyllus fasciatus.
[0262] Insects from the order Thysanura, optionally Lepisma saccharina, Ctenolepisma urbana, and Thermobia domestica.
[0263] Pests from the class Chilopoda, optionally Geophilus spp., Scutigera spp., optionally Scutigera coleoptrata.
[0264] Pests from the class Diplopoda, optionally Blaniulus guttulatus, Julus spp., Narceus spp.
[0265] Pests from the class Symphyla, optionally Scutigerella immaculata.
[0266] Insects from the order Dermaptera, optionally Forficula Auricular ia.
[0267] Insects from the order Collembola, optionally Onychiurus spp., optionally Onychiurus armatus. [0268] Pests from the order Isopoda, optionally Armadillidium vulgare, Oniscus asellus, Porcellio scaber.
[0269] Insects from the order Phthiraptera, optionally Damalinia spp., Pediculus spp., optionally Pediculus hu-manus capitis, Pediculus humanus corporis, Pediculus humanus humanus; Pthirus pubis, Haematopinus spp., optionally Haematopinus eurysternus, Haematopinus suis; Linognathus spp., optionally Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp. [0270] Most preferably pests include, but are not limited to, Lepidoptera, optionally Helicoverpa spp., Heliothis virescens, Lobesia botrana, Ostrinia nubilalis, Plutella xylo Stella, Pseudoplusia includens, Scirpophaga incertulas, Spodoptera spp., Trichoplusia ni, Tuta absoluta, Cnaphalocrocis medialis, Cydia pomonella, Chilo suppressalis, Anticar sia gemmatalis, Agrotis ipsilon, Chrysodeixis includens; True bugs, optionally Lygus spp., Stink bugs, for example Euschistus spp., Halyomorpha halys, Nezara viridula, Piezodorus guildinii, Dichelops furcatus; Thrips, optionally Frankliniella spp., Thrips spp., Dichromothrips corbettii; Aphids, optionally Acyrthosiphon pisum, Aphis spp., Myzus persicae, Rhopalosiphum spp., Schi-zaphis graminum, Megoura viciae; Whiteflies, optionally Trialeurodes vaporariorum, Bemisia spp. Coleoptera, optionally Phyllotreta spp., Melanotus spp.,Meligethes aeneus, Leptinotarsa decimlineata, Ceutorhynchus spp., Diabrotica spp., Anthonomus grandis, Atomaria linearia, Agriotes spp., Epilachna spp.;
Flies, optionally Delia spp., Ceratitis capitate, Bactrocera spp., Liriomyza spp .; Coccoidea, optionally Aonidiella aurantia, Ferrisia virgate; Anthropods of class Arachnida (Mites), optionally Penthaleus major, Tetranychus spp. ; Nematodes, optionally Heterodera glycines, Meloidogyne sp., Pratylenchus spp., and Caenorhabditis elegans.
[0271] The conjugates described herein and compositions comprising the conjugates described herein can be used in insect control for a plant.
[0272] The conjugates described herein and compositions comprising the conjugates described herein can be used in pest control, optionally insect control, for a plant.
[0273] The plant can be achoccha, amaranth, angelica, anise, apple, arrowroot, arugula, artichoke, globe, artichoke, Jerusalem, asparagus, atemoya, avocado, balsam apple, balsam pear, bambara groundnut, bamboo, banana, plantains, barbados cherry, beans, beet, blackberry, blueberry, bok choy, boniato, broccoli, Chinese broccoli, raab broccoli, Brussels sprouts, bunch grape, burdock, cabbage, cabbage, sea-kale, swamp cabbage, calabaza, cantaloupes, muskmelons, capers, carambola (star fruit), cardoon, carrot, cassava, cauliflower, celeriac, celery, celtuce, chard, chaya, chayote, chicory, Chinese jujube, chives, chrysanthemum, chufa, cilantro, citron, coconut palm, collards, comfrey, corn, Cuban sweet potato, cucumber, cushcush, daikon, dandelion, dasheen, dill, eggplant, endive, eugenia, fennel, fig, galia muskmelon, garbanzo, garlic, gherkin, ginger, ginseng, gourds, grape, guar, guava, hanover salad, horseradish, huckleberry, ice plant, jaboticaba, jackfruit, jicama, jojoba, kale, kangkong, kohlrabi, leek, lentils, lettuce, longan, loquat, lovage, luffa gourd, lychee, macadamia, malanga, mamey sapote, mango, martynia, melon, casaba, melon, honeydew, momordica, muscadine grape, muskmelons, mustard, mustard collard, naranjillo, nasturtium, nectarine, okra, onion, orach, oranges, papaya, paprika, parsley, parsley root, parsnip, passion fruit, peach, plum, peas, peanuts, pear, pecan, pepper, persimmon, pimiento, pineapple, pitaya, pokeweed, pomegranate, potato, sweet potato, pumpkin, purslane, radicchio, radish, rakkyo, rampion, raspberry, rhubarb, romaine lettuce, roselle, rutabaga, saffron, salsify, sapodilla, sarsaparilla, sassafrass, scorzonera, sea kale, seagrape, shallot, skirret, smallage, sorrel, soybeans, spinach, spondias, squash, strawberries, sugar apple, sweet basil, sweet corn, sweet potato, swiss chard, tomatillo, tomato, tree tomato, truffles, turnip, upland cress, water celery, water chestnut, watercress, watermelon, yams, zucchini, or a combination thereof.
[0274] A method of treating an insect infestation in a plant can comprise contacting the plant with a conjugate described herein. The plant can be sprayed, dipped, misted, or a combination thereof for application of the conjugate described herein.
[0275] All references cited in this specification are herein incorporated by reference as though each reference was specifically and individually indicated to be incorporated by reference. The citation of any reference is for its disclosure prior to the filing date and should not be construed as an admission that the present disclosure is not entitled to antedate such reference by virtue of prior invention.
[0276] It will be understood that each of the elements described above, or two or more together can also find a useful application in other types of methods differing from the type described above. Without further analysis, the foregoing will so fully reveal the gist of the present disclosure that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this disclosure set forth in the appended claims. The foregoing an embodiment are presented by way of example only; the scope of the present disclosure is to be limited only by the following claims.
EXAMPLES
EXAMPLE 1 Material and Methods
The materials and methods described herein were used in the Examples that follow.
[0277] Synthesis of Gd3+ doped carbon dots (GdCDs). The synthesis of GdCDs was accomplished with a slight modification to the protocol described by Yu et al. J, Allows Compd. 688: 611-619 (2016). In brief, a reaction mixture was prepared by adding 0.5 g (434 mM) of citric acid (Fisher, 99.7 %), 0.2 g (126 mM) of GdCh (Alfa-Aesar, 99.9%) and 0.17 mL of diethylenetriamine (Alfa-Aesar) into 6 mL of molecular grade water and stirred vigorously. Afterwards, the reaction mixture was transferred to a 10 mL Teflon-lined stainless steel hydrothermal autoclave and heated at 180°C in a mechanical oven for 2 hours. After cooling down, the resulting dark brown dispersion was sonicated for 15 min at 80 kHz and centrifuged to remove large particles. The collected supernatant was filtered through 0.02 pm syringe filters (Anotop, Whatman, Germany) to further remove the large particles. Finally, the GdCDs dispersion was transferred to the dialysis membrane (MWCO: 1 kDa, Spectrum Labs) and dialyzed in molecular grade water for 48 h with regular water changes.
[0278] Synthesis of undoped carbon dots (CDs). The CDs were synthesized by modifying a previously reported protocol. Khan et al. Sci. Rep. 7: 14866 (2017). In a typical synthesis, 2.40 g (40 mM) of urea (99.2%, Fisher) and 1.92 g (10 mM) of citric acid (Fisher, 99.7 %) were dissolved in 2 mL of molecular grade water in an agate mortar. Subsequently, 1.35 mL of ammonium hydroxide (Sigma-Aldrich, 30-33%) solution was added. The resulting reaction mixture was then heated in an oven at 180°C for 1.5 h. After cooling to room temperature, the product was dissolved in 25 mL of molecular grade water and bath sonicated for 1 hour. The obtained dispersion was centrifuged at 4500 rpm for 30 min to remove the large aggregates. Finally, the CDs dispersion was transferred to the dialysis membrane (MWCO: 1 kDa) and dialyzed in molecular grade water for 48 hours with regular water changes.
[0279] Functionalization of GdCDs and CDs with y-cyclodextrin. The functionalization of GdCDs and CDs with y-cyclodextrin was achieved via a slight modification of a previously reported protocol. Santana et al. ACS Nano 16: 12156-12173 (2022). Briefly, both the GdCDs and CDs were diluted to 0.5 mg mL'1 in a 15 mL solution of 10 mM TES buffer (pH 6). Next, 10 pL (967 mM) of l-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC-HC1) aqueous solution (Thermo scientific) and 10 pL (870 mM) of N- hydroxysulfosuccinimide (NHS) aqueous solution (Thermo scientific) were added to the GdCDs and CDs dispersions, and the mixture was stirred for 30 minutes. This was followed by the addition of 10 pL (1.21 M) of 4-carboxyphenylboronic acid (CPBA) (Alfa-Aesar, 97%) solution (prepared in DMSO), which was allowed to react for 3 h at room temperature under vigorous stirring. The resulting CPBA-modified GdCDs and CDs were dialyzed (MWCO: 1 kDa) in a molecular-grade water for 12 h to remove the unreacted CPBA. Subsequently, the pH of the resulting CPBA-modified GdCDs and CDs dispersion was adjusted to 10.5 with NaOH (Sigma-Aldrich, 97%) in 10 mM TES buffer and 15 pL (62.5 mM) of y-cyclodextrin (TCI chemicals, >99%) solution (prepared in DMSO). The mixture then was allowed to react for another 3 h at room temperature under vigorous stirring. Finally, the y-cyclodextrin functionalized GdCDs (y-GdCDs) and CDs (y-CDs) were purified by overnight dialysis in a molecular-grade water.
[0280] Characterization of nanocarriers. The morphology and height profile of GdCDs and y-GdCDs were recorded using a tapping mode of atomic force microscopy (AFM) (Dimension 5000; Veeco, USA). To prepare the AFM samples, a silicon wafer first was washed by dipping in ethanol and acetone for 30 sec each, using a bath sonicator. Subsequently, 5 pL of the respective GdCDs and y-GdCDs dispersion (1 pg mL’1) was dropped on different silicon wafers and dried overnight. The chemical composition of CDs and GdCDs before and after a modification with y-cyclodextrin was investigated using a Nicolet i S50 fourier transform-infrared (FTIR) advanced KBr gold spectrometer equipped with a Smart iTR diamond ATR device. The hydrodynamic size and zeta potential of CDs and GdCDs before and after a modification with y-cyclodextrin were measured using a Malvern Zetasizer Nano ZSP instrument at a temperature of 25 °C. For zeta potential and hydrodynamic size measurements, the respective samples at a concentration of 0.1 mg mL'1 were dispersed in 10 mM TES buffer (pH 7) and 0.1% triton x-100, respectively. The optical absorbance and fluorescence spectra of both CDs and GdCDs before and after a modification with y-cyclodextrin was recorded using a UV-vis spectrophotometer (UV-2600, Shimadzu) and fluorescence spectrophotometer (Horiba PTI QM-400), respectively.
[0281] Quantum yield (QY) calculation. The QY of GdCDs and CDs in an aqueous dispersion (refractive index q = 1.33) was determined by comparing their integrated fluorescence intensity and absorbance values to those of quinine sulfate (Acros organics, 99%) in 0.1 M H2SO4 aqueous solution (refractive index q=l .33). Quinine sulfate serves as a standard with a known QY of 54%. To minimize the impact of reabsorption, the absorbance values of all samples at the excitation wavelength (355 nm) were maintained below 0.1 54 The relative QY was calculated by using the following equation:
Figure imgf000049_0001
where (p is the QY, Grad is the gradient from the plot of integrated fluorescence intensity versus absorbance, and r is the refractive index of the solvent. ST denotes the standard (quinine sulfate) and X denotes the samples (GdCDs / CDs).
[0282] Quantification of y-cyclodextrin fraction in y-GdCDs. The quantification of y- cyclodextrin in y-GdCDs was carried out by studying the interaction of Nile red dye (Sigma- Aldrich), a fluorescent chemical cargo, with y-cyclodextrin. y-cyclodextrin can form an inclusion complex with several chemical cargoes. The interaction of Nile red dye with y- cyclodextrin was investigated by measuring changes in fluorescent intensity of Nile red dye in the presence of y-cyclodextrin. Due to poor solubility of Nile red dye and y-cyclodextrin in an aqueous medium, a stock solution of Nile red dye (350 pM) and y-cyclodextrin (400 pM) was prepared in dimethyl sulfoxide (DMSO) (Alfa-Aesar, 99.9%). A 1 mL reaction mixture (30% DMSO in 10 mM (pH 7) TES buffer) containing a fixed amount of dye (15.7 pM) and varying concentrations of y-cyclodextrins (0, 1, 2, 4, 8, 12, 16, 24, 32, and 50 pM) was prepared and incubated for 1 h at room temperature with shaking. The fluorescence spectra were measured after transferring 200 pL from each sample to a 96-well plate and exciting the mixture at 585 nm wavelength. Based on these spectra, a calibration curve was generated by fitting the non-linear relationship between changes in Nile red dye fluorescence intensity (I- lo/Io) and different concentrations of y-cyclodextrin. To quantify the fraction of y- cyclodextrin in y-GdCDs, 100 pg of y-GdCDs was incubated with Nile red dye (15.7 pM) for 1 hour at room temperature with shaking. The fluorescence intensity of the mixture then was measured after exciting at 585 nm and was fitted into the calibration curve to determine the percentage of y-cyclodextrin in y-GdCDs.
[0283] Plant growth. Soybean (Glycine max) seeds were sown in plastic pots (2.5 x 2.5 x 3.5 mm3) containing standard mixed soil (Sunshine, LC1 mix) and transferred to LED growth chambers (HiPoint). Growth chamber conditions were 250 pmol nr2 s'1 PAR, 23/21 °C day/night temp., 60% humidity, and 14/10 h photoperiod. Plants were watered once every two days.
[0284] Loading of rhodamine 6 G (R6G) dye in y-GdCDs. To load R6G, a 10 pL portion of a 1 mM aqueous solution of R6G was added to a 1 mL of y-GdCDs dispersion (0.1 mg mL'1) prepared in a 10 mM TES buffer (pH 7). This resulted in a final concentration of R6G at 0.01 mM. The reaction mixture then was reacted by shaking in a microplate shaker at 550 rpm for 3 hours, which resulted in the formation of the y-GdCDs-R6G inclusion complex. The formation of y-GdCDs-R6G inclusion complex was characterized through absorbance and fluorescence spectroscopy. Subsequently, y-GdCDs-R6G complex was utilized to investigate its interactions with soybean leaves.
[0285] Confocal imaging of y-GdCDs-R6G nanocarriers in leaves. Soybean leaf samples were imaged using a Zeiss 880 inverted confocal laser scanning microscope (CLSM). The first true leaves (two-week-old plants) were treated with 5 pL of y-GdCDs- R6G nanocarriers dispersion (prepared in 0.1% triton x-100) and incubated for 3 hours at room temperature. The leaves treated with 0.1% triton x-100 served as a control. After incubation, 6-mm leaf disks were cut from the treated leaves with the help of a cork borer and placed in a Carolina observation gel chamber (~1 mm in thickness) created on a microscope slide (Corning 2948-75x25). The chamber was filled with perfluorodecalin (PFD, 90%, Acros organics) and sealed with a coverslip (VWR). The CLSM imaging settings were as follows: 20x objective lens; 355 nm laser for y-GdCDs excitation, 488 nm for R6G excitation, and 633 nm laser for chloroplast excitation; z-stack section thickness = 2 pm; line average = 4; PMT detection range was set to 400-500 nm for y-GdCDs, 550-640 nm for R6G, and 650-750 nm for chloroplast autofluorescence. The colocalization of y-GdCDs and R6G with chloroplasts in equidistantly separated images in confocal image overlays was performed using the Coloc 2 function in Fiji software. The correlation between the fluorescence signals was analyzed using Pearson’s overlap coefficient analysis. At least three soybean plants were used for CLSM analysis from the leaf surface to deep in the mesophyll cells.
[0286] Insect rearing. Nezara viridula were reared. Briefly, insects were maintained on fresh organic green bean pods (Phaseolus vulgaris L.), raw peanuts (Arachis hypogaea L.), and raw sunflower seeds (Helianthus annuus L.). Late instar nymphs and adults also were provided bouquets of alfalfa plants and soybean plants (Glycine max). All the life stages were maintained in an insectary set at 30°C, 70% relative humidity, and 16-hour photoperiod. [0287] Characterization of N. viridula tarsi. The optical properties of adult insect tarsi were characterized using CLSM. To prepare the samples for CLSM, the adult insects were anesthetized using CO2 and their tarsi were carefully removed and mounted on glass slides using glycerol (mounting medium). The CLSM imaging settings were as follows: lOx wet objective; z-stack section thickness = 4 pm; line average = 4; PMT detection gain = 500; and focal plane pinhole size = 1.5 airy units. The tarsi were illuminated with lasers at three distinct wavelengths, 355 nm, 488 nm, and 561 nm, and the emitted fluorescence was collected between 400-500, 500-600, and 600-700 nm wavelengths, respectively. The photomultiplier tube (PMT) detection gain was set to 500 and the focal plane pinhole size to 1.5 airy units. The images were acquired using the Zeiss Zen software and processed using Fiji software (Image- J).
[0288] The tarsal surface of bugs was characterized using a tabletop scanning electron microscope (SEM) (Hitachi TM4000). In brief, the tarsi of anesthetized adult insects were cut-off and washed several times with lx phosphate buffer (pH 7.0) to remove the surface contamination. The tarsi then were fixed in formalin for 2 h at room temperature and washed again multiple times with lx phosphate buffer (pH 7.0). Afterwards, the samples were dehydrated in a graded series of ethanol (30, 50, 75, and 95%) and sputter coated with goldpalladium. Finally, the samples were observed under the SEM at an accelerating voltage of 15 KV.
[0289] Loading of Nile red dye in y-GdCDs. Nile red was loaded into y-GdCDs nanocarriers using a slight modification of the previously reported method. Briefly, 0.05 mg of Nile red dye was dissolved in 0.425 mL DMSO to prepare the Nile red dye solution, which then was added dropwise to 1 mL of y-GdCDs aqueous dispersion (1 mg) under stirring and left to react for 12 hours at room temperature. The resulting y-GdCDs-Nile red dye composite was dialyzed in water (MWCO: 1 kDa) for 12 hours to remove the free dye. The quantification of dye in y-GdCDs was determined by transferring 140 pL of the sample to a 96-well plate and mixing with 60 pL DMSO (30% DMSO). The fluorescence intensity of the sample was measured upon excitation at 585 nm and fitted into the calibration curve for the dye quantification.
[0290] Fluorescent chemical cargo delivery by y-GdCDs nanocarriers into N. viridula tarsi. The inventors investigated y-GdCDs nanocarriers mediated delivery of fluorescent chemical cargoes (Nile red dye) into
Figure imgf000051_0001
viridula tarsi by CLSM analysis. Briefly, 250 pL of nanocarrier (2.2 mg mL'1) containing 7 pg of Nile red dye was dispersed in 0.1% triton x-100 and evenly sprayed onto petri dishes using an airbrush. Subsequently, adult stink bugs were placed into the treated dishes and incubated for 16 h. Following incubation, the stink bugs were anesthetized using CO2 and their tarsi were removed. The tarsi were washed three times with 50% acetone (by dipping tarsi for 15 seconds each time) to remove any particles adhering to the tarsal surface. The washed tarsi were embedded in an optimal cutting temperature (OCT) compound and frozen at -20°C inside a cryostat. The frozen sample was used to make 50 pm tarsal sections from the proximal and distal end of the basitarsus (first tarsal segment (T 1 )). The sections then were transferred to microscope slides (Corning 2948- 75x25), mounted with glycerol, covered with coverslips (VWR), and the edges of the coverslip were sealed with nail polish before being observed under an inverted confocal microscope. The CLSM imaging settings were as follows: 40x wet objective; 488 nm laser for tarsi excitation and 561 nm laser for Nile red excitation; z-stack section thickness = 1 pm; line average = 4; PMT detection gain = 500; focal plane pinhole size = 1.5 airy units; PMT detection range was set 500-600 nm for tarsi autofluorescence and 600-700 nm for Nile red dye. For comparison, 250 pL of only Nile red dye solution (containing 7 pg dye) was applied to the insects in a similar way as the y-GdCDs nanocarriers treatment mentioned above. The Nile red dye solution was prepared by transferring 0.1 mL from dye stock solution (2.8 mg mL'1, prepared in DMSO) to 9.9 mL of 0.1% triton x-100 solution.
[0291] Uptake of y-GdCDs nanocarriers in N. viridula tarsi. The uptake of y-GdCDs nanocarriers to N viridula tarsi was evaluated by inductively coupled plasma - optical emission spectrometry (ICP-OES). In brief, 250 pL (2 mg mL'1) of the nanocarrier dispersion (prepared in 0.1% triton x-100) was evenly sprayed onto each of 10 petri dishes using an airbrush. Subsequently, two adult stink bugs were placed in each treated dish and incubated for 16 hours. The stink bugs then were collected and their tarsi were removed after being anesthetized using CO2. All of the collected tarsal samples were mixed and washed three times with 0.01 M HNO3 and molecular-grade water to remove any particles adhering to the tarsal surface. The tarsi samples then were digested in a metal-grade acidic mixture containing 1 mL HNO3, 0.4 mL HC1, and 0.1 mL H2O2 using a microwave. The digested samples were diluted to 10 mL using molecular-grade water and analyzed using ICP-OES to detect the Gd signal from y-GdCDs.
[0292] Loading of insecticide Al in y-CDs. A hydrophobic insecticide (Insecticide A) with greater than 99% purity was provided by the BASF corporation, North Carolina, USA. To load the insecticide Al, a 10 pL portion from 10 mg mL'1 Al stock (prepared in N-Methyl- 2-pyrrolidone (NMP, Thermo scientific, 99%)) was added to 1 mL of y-CDs aqueous dispersion (0.32 mg mL'1). The reaction mixture then was reacted by stirring at 750 rpm for 6 h, which resulted in the formation of y-CDs-AI inclusion complexes. After that, the loaded sample was transferred to a separating funnel, and to remove any free Al, the sample was washed by passing 1 mL of dichloromethane (DCM) through the sample three times (Acros Organics, 99.9%). Subsequently, the Al present in the y-CDs were extracted in DCM through liquid-liquid extraction and quantified by a calibration curve generated by measuring the absorbance of insecticide standards at 315 nm using UV-vis spectrophotometer. It is noted that the use of DCM as an extraction solvent is based on the high solubility of the Al in DCM, as indicated by the manufacturer's recommendations. The loading capacity (LC) of nanocarriers was calculated by using the following equation:
LC (wt.%) = (weight of loaded insecticide/total weight of nanocarrier) x 100% [0293] Nezara viridula mortality assay. The mortality caused by y-CDs-AI was evaluated on freshly harvested soybean leaves. For this study, trifoliate soybean leaves with similar biometric parameters were collected from 20-30-day-old soybean plants that were cultivated in the growth chambers (described herein). To ensure uniformity, the surface area of all the leaves was measured using a portable area meter (LLCOR Biosciences, LI-3000). The collected leaves were transferred to freshly prepared 1% agar (Fisher scientific) plates. To prevent microbial growth, the agar media was mixed with 30 ppm of streptomycin (Sigma- Aldrich) and 40 ppm of benzimidazole (Sigma- Aldrich) before pouring. After that, the agar plates with leaves were randomly divided into 4 different groups, with each group consisting of 10 plates (40 total plates per replicated). Each group was subjected to specific treatments including y-CDs alone, Al alone, y-CDs-AI, and 0.1% triton x-100. Prior to spraying, all the treatment samples were mixed with 0.1% triton x-100. The treatments were applied to the leaves by spraying an optimized volume of 0.7 mL using an airbrush for 15 sec. For the y- CDs-AI and Al alone groups, the amount sprayed was equivalent to having 7 pg Al (10 ppm, an optimized concentration). After spraying, the leaves were allowed to air dry and then transferred to fresh agar plates to avoid the direct exposure of insects to Al present on the agar surface not covered with leaf. Based on leaf area calculations, the sprayed amount of Al on leaf surface in both the treatments was calculated to be ~3 pg. Subsequently, 1-4 days old adult stink bugs were randomly placed in each agar plate, with each group consisting of 10 insects (composed of 5 males and 5 females). The mortality of the stink bugs in each group was determined every 24 h for a period of 96 h. Three independent replications of all treatments were conducted. It is worth noting that placing the leaf on agar plates not only maintains leaves freshness, but also creates moisture on the leaf surfaces (Figure 17), which may serve as a medium for the uptake of nanocarrier present on leaf surface through the stink bug tarsi. These conditions mimic the open field environment, where the soybean leaf surface, particularly in the morning, is often covered with dew.
[0294] To confirm the delivery of Al mediated by y-CDs-AI and Al alone to N. viridula through their tarsi, a follow-up experiment was conducted in which the stylets of these test insects were carefully removed using scissors. Following the stylet removal, the insects were subjected to the different treatments as mentioned above, and their mortality was observed every 24 hours for 96 hours. [0295] Statistical analysis. The data were plotted using Origin software (Origin Pro 8.5 Corporation, U.S.) and analyzed using GraphPad Prism 8.0 software. Experiments were conducted in triplicates, and the descriptive statistics are presented as the mean and standard error of the mean (SEM). A two-tailed Student t-test was conducted at a 95% confidence level to compare the means and SEM of two independent groups (Figure 5C and Figures 6C, 6D). To compare the mean and SEM of one variable across three or more independent groups, a one-way ANOVA (analysis of variance) with Tukey's post hoc tests was performed at a 95% confidence level (Figure 6A and B). Absence of asterisks signifies a lack of significant difference. Mantel-Cox pairwise comparison was performed between the survival of stink bugs after treatment with different formulations and the significant difference was calculated at a confidence level of 95% using Kaplan-Meier statistics (Figure 15).
EXAMPLE 2 Synthesis and characterization of nanocarriers
[0296] The inventors synthesized and functionalized GdCDs and CDs with y-cyclodextrin to generate nanocarriers for improving the delivery efficiency of insecticide active ingredient (Al) to stink bugs (Figures 7A-7B, 2A). GdCDs and CDs were coated with boronic acids via the formation of an amide bond between amine groups of CDs and carboxyl groups of 4- carboxyphenyl boronic acid using EDC/NHS coupling. The boronic acid functionalized GdCDs and CDs were tethered covalently to the y-cyclodextrin through the formation of cyclic boronic ester bond between the boronic acid and cis-diols of y-cyclodextrin, resulting in y-GdCDs and y-CDs, respectively. The morphology and thickness of GdCDs and y-GdCDs were analyzed using AFM (Figure 2B, C). The nanoparticles exhibited spherical shapes with a size distribution in a range of 4-8 nm.
[0297] After functionalization with y-cyclodextrin, y-GdCDs showed an increase in thickness from 3 nm to 6 nm (Figure 2B). This finding is consistent with a previous report of an increase in the lateral height of carbon quantum dots following cyclodextrin modification. Dynamic light scattering analysis revealed that the hydrodynamic size of GdCDs (5.6 ± 0.8 nm) and CDs (4.7 ± 0.3 nm) significantly increased after y-cyclodextrin functionalization to 7.6 ± 0.6 nm (P < 0.05) and 7.4 ± 0.5 nm (P < 0.005) for y-GdCDs and y-CDs, respectively (0.1% triton x-100) (Figure 2D), which could be due to presence of organic layer. Similar increases in the size of CDs and metal NPs after functionalization with cyclodextrins have been reported previously. The relatively high zeta-potential of GdCDs and CDs showed a value of -23.6 ± 1.1 mV and -37 ± 1.4 mV (TES buffer, pH 7) (Figure 2E), respectively, can be attributed to the presence of abundant carboxyl groups on their surface. However, after functionalization with y-cyclodextrin, the zeta-potential of y-GdCDs and y-CDs decreased in magnitude to -15 ± 1.2 mV (P < 0.001) and -12.6 ± 0.7 mV (P < 0.0001), respectively, similar to previous reports for carbon dot nanocarriers. The measured values are in close proximity to the reported zeta-potential of cyclodextrin alone, suggesting that y-cyclodextrin effectively masked the negatively charged groups on the surface of GdCDs and CDs. Both the hydrodynamic size and zeta-potential measurements indicated nearly identical physicochemical characteristics of y-GdCDs and y-CDs. The presence of cyclodextrin derivatives was also confirmed by the FTIR analysis (Figure 2F). The spectrum of GdCDs and CDs depicted the signature bands at 1180 cm'1, 1355 cm'1, 1635 cm'1 and a broad peak between 3200-3600 cm'1 corresponding to the C-N stretching vibration, O-H bending vibrations, C=O stretching vibrations, and O-H and N-H stretching vibrations, respective. Following modifications with 4-carboxyphenyl boronic acid (CPBA) and y-cyclodextrin, the inventors observed additional peaks at 1584 cm'1 and 1042 cm'1 corresponding to the amide bond formed between the carboxyl groups of CPBA and amine groups of CDs and glycosidic vibration (C-O-C) denoting y-cyclodextrin, respectively, in the spectra of y-GdCDs and y- CDs, confirming successful functionalization.
[0298] The optical properties of nanocarriers were characterized using absorbance and fluorescence spectroscopy. GdCDs and y-GdCDs showed absorbance maxima at 349 nm and 350 nm, respectively (Figure 2G), which is attributed to the n-7t* transition of C=O bands, indicating the presence of carboxyl/carbonyl groups on the surface of GdCDs and y-GdCDs. The fluorescence spectra of GdCDs and y-GdCDs upon excitation at 355 nm showed the emission maxima at 438 nm and 441 nm, respectively (Figure 2H). The red shift in the emission maxima of y-GdCDs can be ascribed to the quantum size effect. Further, y- cyclodextrin functionalization caused the quenching of GdCDs fluorescence intensity (measured at the same concentration of Gd) by 1.5 times. Similar quenching in the fluorescence intensity of CDs after modification with cyclodextrin and other capping agents has been observed before. In contrast, CDs and y-CDs showed two absorbance peaks at 334 and 394 nm (Figure 8A), which can be assigned to the n-7t* transition of C=O bands and formation of conjugated sp2 carbon cores in CDs, respectively. Furthermore, both CDs and y- CDs demonstrated fluorescence emission maxima at 450 nm (Figure 8B). Using quinine sulfate (QY= 54%) as a reference, the GdCDs showed a relatively high quantum yield (QY) (59%) as compared to CDs (1.7%), which can be attributed to the disruptive effect of Gd on the carbon rings, leading to the creation of new energy traps for emission. This high QY along with the presence of traceable Gd element in GdCDs allowed fundamental research about their interactions with plant leaf surface by confocal microscopy and uptake in stink bug tarsi by ICP-OES analysis.
[0299] The fraction of y-cyclodextrin in y-GdCDs and binding to fluorescent chemical cargoes was determined by investigating the host-guest interaction between Nile red dye and y-cyclodextrin. To conduct this study, the inventors determined the solubility of Nile red dye in varying DMSO concentrations in aqueous solution through spectrophotometric analysis. With a decrease in DMSO percentages from 100% to 50%, the dye solution showed a red shift in the absorbance maxima (from 550 nm to 582 nm), but without compromising in the absorbance intensity (Figure 9A). However, a significant decrease in the dye absorbance in 30% DMSO was observed, which may be attributed to the aggregation of dye with decreasing DMSO percentage. Further, the dye aggregation was observed through a color change of the solution (from pink-blue-transparent) with decreasing DMSO percentage (Figure 9B). The aggregation of dye is reported to be prevented by forming the inclusion complex with cyclodextrins; therefore, a 30% DMSO solution containing fixed amounts of dye and varying amounts of y-cyclodextrin was used to study the host-guest interactions based on the changes in dye fluorescence intensity.
[0300] The inventors observed a gradual increase in the emission intensity of dye with increasing y-cyclodextrin concentration from 0 pM to 24 pM and final attainment of a plateau at 32 pM (Figure 21). This phenomenon is attributed to the increase in dye solubility facilitated by the formation of an inclusion complex with y-cyclodextrin. Using a calibration curve generated by fitting the non-linear relationship between changes in dye fluorescence intensity (I-Io/Io) and different concentrations of y-cyclodextrin (Figure 2J), the fraction of y- cyclodextrin in y-GdCDs was calculated to be 11.8 wt.%. Considering a 1 : 1 host-guest stoichiometry, the content of Nile red dye in y-GdCDs was calculated to be 3 wt.%.
EXAMPLE 3
Restricted nanocarrier and chemical cargo translocation across the plant leaf surface [0301] The inventors designed nanocarriers and nanoformulations that restrict the translocation across the leaf surface for increasing the availability of active ingredients (Ais) to stink bugs. The cuticle and stomatai pores on the leaf epidermal layer act as the main pathways for the uptake of nanoparticles (NPs) to plant leaves. Various physicochemical properties of NPs, for example, size, charge, hydrophobicity and aspect ratio affect their uptake and translocation in plants. The surfactant surface tension in nanoformulations also affects the uptake of NPs across the leaf surface.
[0302] To investigate the translocation of nanocarriers and their chemical cargoes on the plant leaf surface, y-GdCDs were loaded with R6G dye (y-GdCDs-R6G) (Figures 10A-10B). Soybean leaves treated with y-GdCDs-R6G (0.1% triton x-100), displayed fluorescence from both y-GdCDs (cyan) and R6G dye (yellow) from the epidermal surface but were not observed inside leaf mesophyll tissue containing chloroplasts (Figure 3 A). Control leaves treated solely with 0.1% triton x-100 displayed no background autofluorescence in the y- GdCDs nanocarrier and R6G emission channels. Orthogonal views of z-stack images (Figure 3B), indicated no overlap of y-GdCDs and R6G dye fluorescence with chloroplast autofluorescence. However, a significant colocalization between y-GdCDs and R6G dye fluorescence was observed, indicating that nanocarriers effectively retain the fluorescent cargo and prevent its release onto the leaf surface. A Pearson’s overlap coefficient analysis confirmed no correlation (P = 0) between the overlap of y-GdCDs and R6G dye fluorescence with the chloroplast autofluorescence observed in the same plane of merged images.
However, a positive correlation (P = 1) was observed between the overlapping of y-GdCDs fluorescence and R6G dye fluorescence. Reconstructed 3D images from z-stacks also show the presence of nanocarrier and R6G dye fluorescence over the leaf surface (Figure 3C). [0303] Confocal microscopy analysis indicates that y-GdCDs-R6G nanocarriers preferentially localize on the leaf epidermal surface, which could be attributed to cuticle size exclusion limit, surfactant surface tension, or repulsive electrostatic interactions with the cell wall. The leaf cuticle possesses <2 nm hydrophilic pores, which may impose a size exclusion limit and prevent the uptake of ~8 nm size y-GdCDs nanocarriers. In addition, the high surface tension of triton x-100 could prevent the uptake of y-GdCDs through stomatai pores into the leaf mesophyll. A CD dispersion in triton x-100 surfactant, with a high surface tension of 30 mN/m, prevented CDs uptake in both dicot and monocot plants; whereas CDs dispersion in Silwet L-77 surfactant, with a low surface tension of 22 mN/m, allowed CD uptake. Repulsion electrostatic interactions between the negatively charged cell walls and negatively charged y-GdCDs may also inhibit nanocarrier translocation across the leaf epidermis. Pectin in plant cell walls has a negative charge, exhibiting a higher affinity towards positively charged NPs that could facilitate their passive translocation acting as a cation exchange membrane. Furthermore, based on NP -leaf interaction empirical models, NPs with a charge below +15 mV exhibited less foliar uptake efficiencies into mesophyll tissue. This nanocarrier and nanoformulation design carrying loaded active ingredient (Al) prevents their uptake into soybean leaves making them readily available to stink bugs on the leaf surface.
EXAMPLE 4
Fluorescent chemical cargo delivery to stink bugs tarsi by nanocarriers
[0304] To assess the nanocarrier mediated delivery of a model fluorescent chemical cargo to stink bug tarsi, the inventors characterized the optical and morphological properties of N. viridula tarsi using confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). Upon excitation at 355 nm and 488 nm wavelengths, the tarsi exhibit bright autofluorescence in both UV-blue (400-500 nm) and green-yellow (500-600 nm) visible spectra regions (Figure 4A). The UV-blue fluorescence indicates exoskeleton structures that predominantly consist of the soft and highly elastic protein known as resilin; whereas green-yellow fluorescence indicates exoskeleton structures composed of weakly or non-sclerotised chitinous material (Figure 4A). However, upon excitation at 561 nm wavelength, the tarsi do not exhibit any autofluorescence in the orange-red fluorescence region (600-700 nm). Similarly, 50 pm cryostat sections of tarsi show bright autofluorescence at 355 nm and 488 nm excitation wavelengths in UV-blue and green-yellow fluorescence range, but no autofluorescence at 561 nm excitation within the orange-red fluorescence range (Figure 11). This no background fluorescence range offers fluorescence spectra window upon 561 nm excitation for imaging nanocarrier mediated cargo delivery of a fluorescent chemical cargo into the insect tarsi.
[0305] To determine the morphological features of the tarsal surface, the inventors characterized the surface of N viridula tarsi using SEM (Figure 4B) including the distribution and size of tarsal pores and glands that could act as pathways of the nanocarrier entry through the tarsi. The tarsi of N viridula are composed of three tarsal segments: basitarsus (Tl), mediotarsus (T2), and distitarsus (T3) (Figure 4B-i). Tl and T3 are larger than the T2 segment, where Tl serves as a hairy adhesive pad with setae on its ventral side. The T3 segment carries a pretarsus (PR) consisting of two curved claws (CL), two pulvilli (P), an unguitractor plate (U), and a pair of paraempodia (PA) (Figure 4B-ii). The claws are situated dorsally, while the pulvilli and paraempodia are located ventrally. The paraempodia emerge from the distal surface of the unguitractor plate, whereas the pulvilli originate from the claws. A small plate located at the basal part of each pulvillus is known as the basipulvillus (BP). At lower magnification, the ventral surface of the pulvilli appears smooth (Figure 4B-iii), but upon closer examination (Figure 4B-iv), it becomes apparent that it contains grooves running parallel to the longitudinal axis of the pretarsus. At higher magnification, the ventral surface of T1 contains -150 nm sized pores (indicated by red arrows) (Figure 4B-v), and several pore canals running through the cuticle (Figure 4B-vi). The inset in Figure 4B-vi shows the presence of clear sub-micron size openings. The ventral side of the pulvillus has also been reported to possess numerous pores on the epicuticle surface. Several of these structures and surfaces come in contact with the leaf surface, including ventral surfaces of the distal portions of the pulvilli, paraempodia, claw tip, and basitarsus. These sub-micron size pores in stink bug tarsi could potentially facilitate the uptake of nanosize CDs applied on the leaf surface, thereby offering the possibility of delivery of insecticide active ingredient (Al) through the tarsi.
[0306] To determine nanocarrier mediated delivery of chemical cargoes to stink bug tarsi by confocal microscopy, The inventors loaded y-GdCDs nanocarriers with the fluorescent Nile red dye (y-GdCDs-Nile red). Nile Red dye was chosen for its non-polar nature like many insecticide AIs, and it possesses excitation and emission maxima at 561 nm and 635 nm, respectively, which allowed imaging in the insect tarsi without background autofluorescence (see Figure 4A). Insect tarsi treated solely with 0.1% triton x-100 display bright autofluorescence (UV-blue range) when excited at 488 nm, whereas no background autofluorescence was observed in the Nile Red emission channels (Figures 5A-5B).
However, the confocal images of T1 sections from proximal and distal ends of stink bugs treated with Nile Red and y-GdCDs-Nile Red demonstrated the uptake of both Nile Red dye alone and delivered by y-GdCDs (Figures 5A-5B).
[0307] The inventors selected T1 for the uptake analysis because this segment along with distal portions of the pulvilli are in direct contact with the leaf surface during stink bug walking, and the highly curved pulvilli impede preparation of sections for imaging. Tarsal sections (Tl) prepared from both proximal and distal end after treatment with Nile red and y- GdCDs-Nile red, confirmed colocalization of Nile red pixels with the tarsal autofluorescence pixels throughout the 50 pm z-stack. The average fluorescence intensity (n = 3) of Nile red dye in both the Nile red and y-GdCDs-Nile red treated insect sections was quantified using ROI manager tools in Image-J software (Figure 5C). Insects treated with y-GdCDs-Nile red nanocarriers exhibit -2.6-fold higher fluorescence intensity of Nile red in both the proximal and distal ends of the tarsi than insects treated solely with Nile red (P < 0.05), demonstrating the capacity of nanocarriers to enhance the delivery of a chemical cargo.
[0308] The enhanced uptake could be attributed to the presence of sub-micron sized pores and glands on the tarsal surface (Figure 4B-v,vi), which facilitates greater uptake of nanosized y-GdCDs-Nile red compared to Nile red dye alone. Furthermore, encapsulation of Nile red in y-GdCDs may increase its solubility and thus enhance bioavailability. Similarly, nanocarrier mediated delivery of chemical cargoes has been reported in plant and non-insect animal organisms. The uptake of y-GdCDs in stink bugs was also determined using ICP-OES based on the measurement of the Gd content. Gd was detected in the tarsi of insects treated with nanocarriers, whereas no Gd signal was observed in untreated insects, providing further evidence of y-GdCDs uptake (Figure 5C). The findings demonstrate that the conjugates described herein can overcome insect Al delivery barriers through the sting bug tarsi.
EXAMPLE 5
Enhanced mortality efficacy of insecticide Al delivered by y-CDs
[0309] For determining the efficacy of nanocarrier mediated delivery of Al in agricultural applications, the inventors synthesized undoped nanocarriers without Gd (y-CDs) and loaded them with an insecticide (BASF 3859656) from BASF Corporation (y-CDs-AI). The formation of inclusion complexes using cyclodextrins can offer several advantages to the guest Al molecules, for example enhanced solubility, stabilization of the molecule in solution, and reduced losses due to volatilization. After loading the Al, the y-CDs- Al exhibited no notable change in the hydrodynamic size (7.0 ± 0.4 nm) (Figure 12) and zeta potential (-14.9 ± 1.3 mV) in comparison to y-CDs (Figures 2D, 2E). This can be attributed to the efficient complexation of Al with y-CDs, without any significant adsorption occurring on the y-CDs surface. The FTIR spectrum of y-CDs-AI shows the appearance of several new peaks that match the peaks of bare Al, in addition to the peaks corresponding to y-CDs (Figure 13). However, a few Al peaks at 2966, 1726, and 1350 cm’1 were shifted to 2950, 1716, and 1337 cm’1, respectively, in the y-CDs-AI spectrum. Additionally, in comparison to the y-CDs spectrum, the inventors observed the glycosidic vibration (C-O-C) peak of y- cyclodextrin in the spectrum of y-CDs-AI had shifted from 1042 cm’1 to 1072 cm’1. These spectroscopic changes indicate the inclusion complex formation between y-CDs and Al. The loading capacity of y-CDs for the Al was quantified as 14.4 ± 1.5%. The formation of the inclusion complex between y-CDs and Al is primarily attributed to hydrophobic interactions between the inner hydrophobic cavity of y-cyclodextrin and the hydrophobic active ingredient (Al). The loading and delivery of hydrophobic Al in y-CDs-AI nanoformulations could improve Al mortality efficacy for N. viridula due to the enhanced solubility and stabilization of the hydrophobic Al. [0310] The efficacy of the y-CDs-AI nanoformulation compared to Al (active ingredient) alone was tested by exposing insects on soybean leaves sprayed with 0.1% triton x-100 alone, y-CDs alone, active ingredient (Al) alone, and y-CDs-AI (0.1% triton x-100) (Figure 14). All treatments using Al were used at a concentration of 10 ppm. After 48 and 72 h post treatment, the y-CDs-AI caused approximately 1.75-fold higher bug mortality compared to Al alone (Figure 6A). At 96 h, the y-CDs-AI and Al alone caused 85% and 60% mortality, respectively, demonstrating a 25% greater mortality using y-CDs-AI. A Kaplan-Meier survival analysis test confirmed that y-CDs-AI caused significant higher mortality of stink bugs compared to Al alone (Figure 15). Little to no mortality was observed in the triton x- 100 treatment and the y-CDs treatment (Figure 6A). Overall, these results indicate the superior efficacy of the developed nanoformulation for N. viridula mortality compared to Al alone. The higher mortality with y-CDs-AI could be attributed to the effectiveness of y-CDs- AI entering the stink bugs through their tarsal pores and delivering significantly higher levels of Al compared to Al alone.
[0311] To test this hypothesis, the inventors evaluated the efficacy of y-CDs-AI compared to y-CDs alone and Al alone in insects after removing their stylets (Figures 16A-16B). The removal of the stylet reduced insect mortality by 50%, likely due to the reduction of Al entering the insect's body through the mouth feeding pathway. After 48 hour treatment, the y- CDs-AI resulted in a -23% stink bug mortality, while very low mortality was observed in the Al alone treatment (Figure 6B). After 72 and 96 hours, the y-CDs-AI exhibit -35% and -45% higher mortality, respectively, compared to Al (active ingredient) alone. A follow-up experiment compared the efficacy of y-CDs-AI and Al alone on insects with intact stylets and those whose stylets had been removed. Throughout the 96 hour observation period, the y- CDs-AI caused nearly identical mortalities in insects with or without stylets (Figure 6C) strongly suggesting uptake of y-CDs-AI into the tarsi. However, in the Al alone treatment there was -20% (2 -fold) and -18% (1.4-fold) less insect mortality after 72 and 96 hours, respectively, when the stylets were removed (Figure 6D). These unprecedented findings strongly support the hypothesis that the y-CDs-AI nanoformulation delivers Al through the insect tarsi leading to superior efficacy in N viridula mortality compared to Al alone. The consistent efficacy of the nanoformulation, regardless of stylet removal, indicates that the non-classical novel route of delivery through the tarsi is effective in achieving stink bug mortality.

Claims

WHAT IS CLAIMED:
1. A conjugate comprising a cyclodextrin conjugated to a nanoparticle, wherein the cyclodextrin further comprises a pesticide, optionally an insecticide.
2. The conjugate of claim 1, wherein the pesticide is an insecticide.
3. The conjugate of claim 1 or 2, wherein the nanoparticle is a quantum dot, carbon dot, carbon nanotube, silica nanoparticle, lipid nanoparticle, liposome, metal nanoparticle, metal oxide nanoparticle, or a combination thereof.
4. The conjugate of any one of claims 1-3, wherein the nanoparticle is a carbon dot.
5. The conjugate of any one of claims 1-4, wherein the nanoparticle has a size of between about 1 nm and 100 nm.
6. The conjugate of any one of claims 1-5, wherein the nanoparticle has a size of between about 1 nm and 10 nm.
7. The conjugate of any one of claims 1-5, wherein the nanoparticle has a size of between about 1 and 8 nm, 2 and 9 nm, 5 and 7 nm, 4 and 8 nm, or 3 and 9 nm.
8. The conjugate of any one of claims 1-5, wherein the nanoparticle has a size of about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 nm.
9. The conjugate of any one of claims 1-5, wherein the nanoparticle has a size of between about 1 nm and 50 nm, 20 nm and 80 nm, 40 nm and 60 nm, or 75 nm and 95 nm.
10. The conjugate of any one of claims 1-5, wherein the nanoparticle has a size of about 1, 2, 3,
4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29,
30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53,
54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77,
78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 nm.
11. The conjugate of any one of claims 1-10, wherein the nanoparticle has a zeta potential magnitude of about 10 mV to 60 mV.
12. The conjugate of any one of claims 1-11, wherein the cyclodextrin is gamma, beta, alpha cyclodextrin, or a combination thereof.
13. The conjugate of any one of claims 1-11, wherein the cyclodextrin is a gamma cyclodextrin.
14. The conjugate of any one of claims 1-11, wherein the cyclodextrin is a beta cyclodextrin.
15. The conjugate of any one of claims 1-11, wherein the cyclodextrin is an alpha cyclodextrin.
16. The conjugate of any one of claims 1-15, wherein the conjugate comprises between about 1-5 cyclodextrins conjugate to a nanoparticle.
17. The conjugate of any one of claims 1-16, wherein the conjugate comprises about 3 cyclodextrins conjugate to a nanoparticle.
18. The conjugate of any one of claims 1-17, wherein the cyclodextrin forms a molecular cage and the pesticide, optionally an insecticide, is inside the molecular cage.
19. The conjugate of any one of claims 1-18, wherein the cyclodextrin forms a molecular cage and the insecticide is inside the molecular cage.
20. The conjugate of any one of claims 1-19, wherein the insecticide is an AChE inhibitors.
21. The conjugate of claim 20, wherein the AChE inhibitor is aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifosmethyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- (methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxy dem eton-m ethyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion, or a combination thereof.
22. The conjugate of any one of claims 1-19, wherein the insecticide is a GABA-gated chloride channel antagonist.
23. The conjugate of claim 22, wherein the GABA-gated chloride channel antagonist is a cyclodiene organochlorine compound, endosulfan, chlordane, phenylpyrazoles, optionally ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole, or a combination thereof.
24. The conjugate of any one of claims 1-19, wherein the insecticide is a sodium channel modulator.
25. The conjugate of claim 24, wherein the sodium channel modulator is a pyrethroid, optionally acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa- bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bio-resmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta- cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenval erate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin, metofluthrin, momfluorothrin, epsilon- momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa-tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin, transfluthrin, DDT, methoxychlor, or a combination thereof.
26. The conjugate of any one of claims 1-19, wherein the insecticide is a nAChR agonist.
27. The conjugate of claim 26, wherein the nAChR agonist is a neonicotinoid, acetamiprid, clothianidin, cycloxaprid, dinotefuran, im-idacloprid, nitenpyram, thiacloprid, thiamethoxam; 4,5-dihydro-N-nitro-l-(2-oxiranylmethyl)-lH-imidazol-2-amine, (2E-)-l- [(6-Chloropyridin-3-yl)methyl]-N'-nitro-2-pentylidenehydrazinecarboximidamide; l-[(6- Chloropyri din-3-yl)methyl]-7-methyl-8-nitro-5-propoxy- 1 ,2, 3,5,6, 7-hexahydro- imidazo[l,2-a]pyridine; nicotine; sulfoxaflor; flupyradifurone; tritium ezopyrim, fenmezoditiaz, flupyrimin, or a combination thereof.
28. The conjugate of any one of claims 1-19, wherein the insecticide is a Nicotinic acetylcholine receptor allosteric activator.
29. The conjugate of claim 28, wherein the Nicotinic acetylcholine receptor allosteric activator is a spinosyn, optionally Spinosad, spinetoram, or a combination thereof.
30. The conjugate of any one of claims 1-19, wherein the insecticide is a chloride channel activator.
31. The conjugate of claim 30, wherein the chloride channel activator is from the class of avermectins and milbemycins, optionally abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin, or a combination thereof.
32. The conjugate of any one of claims 1-19, wherein the insecticide is ajuvenile hormone mimic.
33. The conjugate of claim 32, wherein the juvenile hormone mimic is hydroprene, kino-prene, methoprene; fenoxycarb, pyriproxyfen, or a combination thereof.
34. The conjugate of any one of claims 1-19, wherein the insecticide is a Miscellaneous multisite inhibitor.
35. The conjugate of claim 34, wherein the Miscellaneous multi-site inhibitor is an alkyl halide including CHiBr, chloropicrin, sulfuryl fluoride, borax, tartar emetic, or a combination thereof.
36. The conjugate of any one of claims 1-19, wherein the insecticide is a Chordotonal organ TRPV channel modulator.
37. The conjugate of claim 36, wherein the Chordotonal organ TRPV channel modulator is afidopyropen, pymetrozine, pyrifluquinazon, or a combination thereof.
38. The conjugate of any one of claims 1-19, wherein the insecticide is a mite growth inhibitor.
39. The conjugate of claim 38, wherein the mite growth inhibitor is clofentezine, hexythiazox, diflovidazin, etoxazole, or a combination thereof.
40. The conjugate of any one of claims 1-19, wherein the insecticide is a Microbial disruptors of insect midgut membrane.
41. The conjugate of claim 40, wherein the microbial disruptors of insect midgut membrane is Bacillus thuringiensis, Bacillus sphaericus, and/or the insecticidal proteins they produce, optionally Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai. Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Abl, or a combination thereof.
42. The conjugate of any one of claims 1-19, wherein the insecticide is an inhibitor of mitochondrial ATP synthase.
43. The conjugate of claim 42, wherein the inhibitor of mitochondrial ATP synthase is diafenthiuron, organotin miticides, optionally azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon, or a combination thereof.
44. The conjugate of any one of claims 1-19, wherein the insecticide is an uncouplers of oxidative phosphorylation via disruption of the proton gradient.
45. The conjugate of claim 44, wherein the uncouplers of oxidative phosphorylation via disruption of the proton gradient is chlorfenapyr, DNOC, sulfluramid, or a combination thereof.
46. The conjugate of any one of claims 1-19, wherein the insecticide is a nAChR channel blocker.
47. The conjugate of claim 46, wherein the nAChR channel blocker is a nereistoxin analogues bensultap, cartap hydrochloride, thio-cyclam, thiosultap-sodium, or a combination thereof.
48. The conjugate of any one of claims 1-19, wherein the insecticide is an inhibitor of the chitin biosynthesis type 0.
49. The conjugate of claim 48, wherein the inhibitor of the chitin biosynthesis type 0 is bistrifluron, chlorfluazuron, difluben-zuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, or a combination thereof.
50. The conjugate of any one of claims 1-19, wherein the insecticide is an inhibitor of the chitin biosynthesis type 1, optionally buprofezin.
51. The conjugate of any one of claims 1-19, wherein the insecticide is a molting disruptor.
52. The conjugate of claim 51, wherein the molting disruptor is Dipteran, cyromazine, or a combination thereof.
53. The conjugate of any one of claims 1-19, wherein the insecticide is an Ecdyson receptor agonist.
54. The conjugate of claim 53, wherein the Ecdyson receptor agonist is methoxyfenozide, tebufenozide, halofenozide, fufeno-zide, chromafenozide, or a combination thereof.
55. The conjugate of any one of claims 1-19, wherein the insecticide is a Octopamin receptor agonist, optionally amitraz.
56. The conjugate of any one of claims 1-19, wherein the insecticide is a Mitochondrial complex III electron transport inhibitor.
57. The conjugate of claim 56, wherein the Mitochondrial complex III electron transport inhibitor is hydramethylnon, acequinocyl, fluacrypyrim, bifenazate, or a combination thereof.
58. The conjugate of any one of claims 1-19, wherein the insecticide is a METI acaricides and insecticide.: fenazaquin, fenpyroximate, pyrimidifen, pyrida-ben, tebufenpyrad, tolfenpyrad, rotenone, or a combination thereof.
59. The conjugate of any one of claims 1-19, wherein the insecticide is a Voltage-dependent sodium channel blocker: indoxacarb, metaflumizone, 2-[2-(4-cyanophenyl)-l-[3- (trifluoromethyl)phenyl]^ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazine- carboxamide, N-(3-chloro-2-methyl_,phenyl)-2-[(4-chlorophenyl)[4-[methyl(methylsul- fonyl)amino]phenyl]_,methylene]-hydrazinecarboxamide, N-[4-chloro-2-[[(l,l- dimethylethyl)amino]carbonyl]-6-methylphenyl]-l-(3-chloro-2-pyridinyl)-3- (fluoromethoxy)-lH-pyrazole-5-carboxamide, 2-[2-(4-cyanophenyl)-l-[3- (trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]- hydrazinecarboxamide.
60. The conjugate of any one of claims 1-19, wherein the insecticide is an inhibitor of acetyl CoA carboxylase.
61. The conjugate of claim 60, wherein the inhibitor of acetyl CoA carboxylase is spirodiclofen, spiromesifen, spirotetramat, spiropidion, spirobudifen, 1 l-(4-chloro-2,6- dimethylphenyl)-12-hydroxy-l,4-dioxa-9-azadispiro[4.2.4.2]tetradec-l l-en-10-one, spidoxamat, or a combination thereof.
62. The conjugate of any one of claims 1-19, wherein the insecticide is a Mitochondrial complex IV electron transport inhibitor.
63. The conjugate of claim 62, wherein the Mitochondrial complex IV electron transport inhibitor is aluminum phosphide, calcium phosphide, zinc phosphide, cyanide, or a combination thereof.
64. The conjugate of any one of claims 1-19, wherein the insecticide is a mitochondrial complex II electron transport inhibitor.
65. The conjugate of claim 64, wherein the mitochondrial complex II electron transport inhibitor is cyenopyrafen, cyflumetofen, cyetpyrafen, pyflubumide, or a combination thereof.
66. The conjugate of any one of claims 1-19, wherein the insecticide is a ryanodine receptormodulator.
67. The conjugate of claim 65, wherein the ryanodine receptor-modulator is chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, fluchlordiniliprole, (R)- 3 -chloro-N 1 - {2-methyl-4-[ 1 ,2,2,2-tetrafluoro- 1 -(trifluoromethyl)ethyl]phenyl } -N2-(l - methyl-2-methylsulfonylethyl)phthalamid, (S)-3-chloro-Nl-{2-methyl-4-[l,2,2,2- tetrafluoro- 1 -(tri fluoromethyl)ethyl]phenyl }-N2-(1 -methyl-2-methylsulfonylethyl jphthal- amide, methyl-2-[3,5-dibromo-2-({ [3-bromo-l -(3-chl orpyridin-2-yl)-lH-pyrazol-5- yl]carbonyl}_,amino)benzoyl]-l,2-dimethylhydrazine-carboxylate; N-[2-(5-amino-l,3,4- thiadiazol-2-yl)-4-chloro-6-methyl_,phenyl]-3-bromo-l -(3-chl oro-2-pyridinyl)-lH- pyrazole-5-carboxamide; 3-chl oro-1 -(3-chl oro-2 -pyridinyl)-N-[2, 4-dichl oro-6-[[(l-cyano-
1-methylethyl)amino]carbonyl]phenyl]-lH-pyrazole-5-carboxamide; tetrachlorantraniliprole; tetraniliprole; tiorantraniliprole; N-[4-chloro-2-[[(l,l-dimethyl- ethyl)amino]carbonyl]-6-methyl-phenyl]-l-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-lH- pyrazole-5-carboxamide; cyhalodiamide; N-[2-(5-amino-l,3,4-thiadiazol-2-yl)-4-chloro-6- methylphenyl]-3-bromo-l-(3-chloro-2-pyridinyl)-lH-pyrazole-5-carboxamide, or a combination thereof.
68. The conjugate of any one of claims 1-19, wherein the insecticide is a Chordotonal organ Modulator, optionally flonicamid.
69. The conjugate of any one of claims 1-19, wherein the insecticide is a GABA gated chlorine channel allosteric modulator.
70. The conjugate of claim 69, wherein the GABA gate chlorine channel allosteric modulator is broflanilide, fluxametamide, isocycloseram, or a combination thereof.
71. The conjugate of any one of claims 1-19, wherein the insecticide is Calcium-activated potassium channel modulator, optionally acynonapyr.
72. The conjugate of any one of claims 1-19, wherein the insecticide is a Mitochondrial complex III electron transport inhibitor QI site, optionally Flometoquin.
73. The conjugate of any one of claims 1-19, wherein the insecticide is Chordotonal organ modulators-undefmed target site, optionally Dimpropyridaz.
74. The conjugate of any one of claims 1-19, wherein the insecticide is afoxolaner, azadirachtin, amidoflumet, ben-zoximate, bromopropylate, chino_,methionat, cryolite, cyproflanilid, dicloromezotiaz, dicofol, dimpropyridaz, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, mivorilaner, modoflaner, piperonyl butoxide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, 11- (4-chloro-2,6-dimethylphenyl)-12-hydroxy-l,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-l l-en- 10-one, 3-(4’-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-l-azaspiro[4.5]dec-3-en-
2-one, 4-cyano-N-[2-cyano-5-[[[2,6-dibromo-4-[l,2,2,3,3,3-hexafluoro-l- (trifluoromethyl )propyl]phenyl]amino]carbonyl]phenyl]-2-methyl-benzamide, 4-cyano-3- [(4-cyano-2-methyl-benzoyl)amino]-N-[2,6-dichloro-4-[l,2,2,3,3,3-hexafluoro-l- (trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide, N-[5-[[[2-chloro-6-cyano-4-
[1,2, 2,3,3, 3-hexafluoro-l-(trifluoromethyl)propyl]phenyl]amino]carbonyl]-2-cy ano-phe- nyl]-4-cyano-2-methyl-benzamide, N-[5-[[[2-bromo-6-chloro-4-[2,2,2-trifluoro-l-hydroxy- l-(trifluoromethyl)ethyl]phenyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2-methyl- benzamide, N-[5-[[[2-bromo-6-chloro-4-[l,2,2,3,3,3-hexafluoro-l-(trifluoromethyl)pro- pyl]phenyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide, 4-cyano-N-[2- cyano-5-[[[2,6-dichloro-4-[l,2,2,3,3,3-hexafluoro-l- (trifluoromethyl)propyl]phenyl]amino]carbonyl]phenyl]-2-methyl-benzamide, l-[2-fluoro-
4-methyl-5-[(2, 2, 2-trifluoroethyl)sulfinyl]phenyl]-3-(tri fluoromethyl)- 1H-1, 2, 4-triazole-5- amine, N-[5-[[[2-bromo-6-chloro-4-[ 1,2,2, 2-tetrafluoro- 1 -(trifluoromethyl)ethyl]phe- nyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide, 4-cyano-N-[2-cyano-
5-[[[2,6-dichloro-4-[ 1,2, 2, 2-tetrafluoro- l-(trifluoro- methyl)ethyl]phenyl]amino]carbonyl]phenyl]-2-methyl-benzamide, actives on basis of bacillus firmus (Votivo, 1-1582); fluazaindolizine; 5-[3-[2,6-dichloro-4-(3,3-dichloroallyl- oxy)phenoxy]propoxy]-lH-pyrazole; N-[5-[[2-bromo-6-chloro-4-[l,2,2,3,3,3-hexafluoro-
1-(trifluoromethyl)-propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl- benzamide; 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[l,2,2,3,3,3-hexafluoro-l -(trifluoro- methyl)-propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; 4-cyano-N-[2-cyano-5- [[2,6-dichloro-4-[l,2,2,2-tetrafluoro-l-(trifluoromethyl)ethyl]phenyl]carbamoyl]_,phenyl]-
2-methyl-benzamide; N-[5-[[2-bromo-6-chloro-4-[ 1 ,2, 2, 2-tetrafluoro- 1 - (trifluoromethyl)ethyl]phenyl]carba_,moyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; 2-(l,3-dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine; 2-[6-[2-(5-fluoro-3-pyridinyl)- 5-thiazoHyl]-2-pyridinyl]-pyrimidine; 2-[6-[2-(3-pyridinyl)-5-thiazolyl]-2-pyridinyl]- pyrimidine; N-methylsul_,fonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; N- methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; l-[(6-chloro-3- pyridinyl)methyl]-l,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro-imidazo[l,2- a]pyridine; l-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-l,2,3,5,6,7- hexahydroimidazo[l,2-a]pyridin-5-ol; N-(3-chloro-2-methylphenyl)-2-[(4-chlorophenyl)[4- [methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide; l-[(6-chloro-3- pyridinyl)methyl]-l,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro-imidazo[l,2- a]pyridine; 2-(3-pyridinyl)-N-(2-pyrimidinylmethyl )-2H-indazole-5-carboxamide; tyclopyrazoflor; sarolaner, lotilaner; N-[4-chloro-3-[[(phenylmethyl)amino]carbo- nyl]phenyl]-l -methyl-3-(l, 1,2,2, 2-pentafluoroethyl)-4-(trifluoromethyl)-lH-pyrazole-5- carboxamide; N-[4-chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-l-methyl-3- (l,l,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)-lH-pyrazole-5-carboxamide; 2-(3- ethylsulfonyl-2-pyridyl)-3-methyl-6-(tri-fluoromethyl)imidazo[4,5-b]pyridine, 2-[3- ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5- b]pyridine; N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-methyl-5-(l,l,2,2,2- pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide, N-[4-chloro-3-[(l- cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-5-(l,l,2,2,2-pentafluoroethyl)-4-(trifluoro- methyl)pyrazole-3-carboxamide; benzpyrimoxan; tigolaner; oxazosulfyl;
[(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl] N-[4-[l-[4- (trifluoromethoxy)phenyl]-l,2,4-triazol-3-yl]phenyl]carbamate; [(2S,3R,4R,5S,6S)-3,4,5- trimethoxy-6-methyl-tetrahydropyran-2-yl] N-[4-[l -[4-(trifluoromethoxy)phenyl]- 1,2,4- triazol-3-yl]phenyl]carbamate; [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy- tetrahydropyran-2-yl] N-[4-[l-[4-(l,l,2,2,2-pentafluoroethoxy)phenyl]-l,2,4-triazol-3- yl]phenyl]carbamate; [(2S,3R,4R,5S,6S)-3,4,5-trirnethoxy-6-methyl-tetrahydropyran-2-yl] N-[4-[l-[4-(l,l,2,2,2-pentafluoroethoxy)phenyl]-l,2,4-triazol-3-yl]phenyl]carbamate; (2Z)- 3-(2-isopropylphenyl)-2-[(E)-[4-[l-[4-(trifluoromethoxy)phenyl]-l,2,4-triazol-3- yl]phenyl]methylenehydrazono]thiazolidin-4-one, (2Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[l- [4-(l,l,2,2,2-pentafluoroethoxy)phenyl]-l,2,4-triazol-3-yl]phe- nyl]methylenehydrazono]thiazolidin-4-one, (2Z)-3-(2-isopro_,pyl_,phenyl)-2-[(E)-[4-[l-[4- (l,l,2,2,2-pentafluoroethoxy)phenyl]-l,2,4-triazol-3- yl]phenyl]methylenehydrazono]thiazolidin-4-one; 2-(6-chloro-3-ethylsulfonyl- imidazo[l,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(6- bromo-3-ethylsulfonyl-imidazo[l,2-a]pyridin-2-yl)-3-methyl-6-(trifluoro- methyl)imidazo[4,5-b]pyridine, 2-(3-ethylsulfonyl-6-iodo-imidazo[l,2-a]pyridin-2-yl)-3- methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(7-chloro-3 -ethyl sulfonyl- imidazo[l,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(7- chloro-3-ethylsulfonyl-imidazo[l,2-a]pyridin-2-yl)-3-methyl-6- (trifluoromethyl )imidazo[4,5-b]pyri dine, 2-(3-ethylsulfonyl-7-iodo-imidazo[l,2-a]pyridin-
2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 3-ethylsulfonyl-6-iodo-2-[3- methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridin-2-yl]imidazo[l,2-a]pyridine-8- carbonitrile, 2-[3-ethylsulfonyl-8-fluoro-6-(trifluoromethyl)imidazo[l,2-a]pyridin-2-yl]-3- methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-7- (trifluoromethyl)imidazo[l,2-a]pyridin-2-yl]-3-methyl-6- (trifluoromethylsulfinyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-7-(trifluoromethyl)imi- dazo[l,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridine, 2-(6-bromo-
3-ethylsulfonyl-imidazo[l,2-a]pyridin-2-yl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine; N- [[2-fluoro-4-[(2S,3S)-2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidin-l- yl]phenyl]methyl]cyclopropanecarboxamide; 2-[2-fluoro-4-methyl-5-(2,2,2- trifluoroethylsulfinyl)phenyl]imino-3-(2,2,2-trifluoroethyl)thiazolidin-4-one; flupentiofenox, N-[3-chloro-l-(3-pyridyl)pyrazol-4-yl]-2-methylsulfonyl-propanamide, cyclobutrifluram; N-[4-chloro-3-[(l-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-4- methylsulfonyl-5-(l,l,2,2,2-pentafluoroethyl)pyrazole-3-carboxamide, cyproflanilide, nicofluprole; l,4-dimethyl-2-[2-(pyridin-3-yl)-2h-indazol-5-yl]-l,2,4-triazolidine-3,5- dione, 2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenyl]imino-3-(2,2,2- trifluoroethyl)thiazolidin-4-one, indazapyroxamet, N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]- N-ethyl-3-methylsulfonyl-propanamide, N-cyclopropyl-5-[(5S)-5-(3,5-dichloro-4-fluoro- phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]isoquinoline-8-carboxamide, 5-[(5S)-5-(3,5- dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-(pyrimidin-2- ylmethyl)isoquinoline-8-carboxamide, N-[l-(2,6-difluorophenyl)pyrazol-3-yl]-2- (trifluoromethyl)benzamide, 5-((lR,3R)-3-(3,5-Bis(trifluoromethyl)phenyl)-2,2- dichlorocyclopropane-l-carboxamido)-2-chloro-N-(3-(2,2-difluoroacetamido)-2,4- di fluorophenyl )benzami de, l-[6-(2,2-difluoro-7-methyl-[l,3]dioxolo[4,5-f]benzimidazol-6- yl)-5-ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile, 6-(5-cyclopropyl-3-ethylsulfonyl- 2-pyridyl)-2,2-difluoro-7-methyl-[l,3]dioxolo[4,5-f]benzimidazole, or a combination thereof.
75. The conjugate of any one of claims 1-19, wherein the insecticide is acephate, fipronil, cypermethrin, bifenthrin, tefluthrin, cyhalothrin, clothianidin, dinotefuran, imidacloprid, thiacloprid, thiamethoxam, sulfoxalor, spinosad, spientoram, emamectin, abamectin, pymetrozine, flonicamid, chlorfenapyr, buprofezin, metaflumizone, cyflumetofen, chlorantraniliprole, tetraniliprole, cyantraniliprole, tiorantraniliprole, pioxaniliprole, fluchlordiniliprole, afidopyropen, dimpropyridaz, fenmezoditiaz, sulfiflumin, broflanilide, cyproflanilide, mivorilaner, modoflaner, umifoxolaner, isocycloseram, indazapyroxamet, spidoxamat, spirotetramat, any insecticide, or biochemical insecticide, or a combination thereof.
76. The conjugate of any one of claims 1-75, wherein the cyclodextrin is a molecular basket.
77. The conjugate of any one of claims 1-76, wherein the cyclodextrin is conjugated to a nanoparticle by a linker.
78. The conjugate of claim 77, wherein the linker is 4-caryboxylphenyl boronic acid (CBPA).
79. The conjugate of claim 77, wherein the linker is 4-aminophenylboronic acid.
80. A composition comprising an effective amount of the conjugate of any one of claims 1-79.
81. The composition of claim 80, wherein the composition further comprises diluents, preservatives, organic solvents, solubilizers, emulsifiers, surfactants, dispersants, preservatives, colorants, fillers, diluents, binders, glidants, lubricants, di sint egrants, antiadherents, sorbents, coatings, wetting agents, penetrants, vehicles, and combinations thereof.
82. The composition of claim 80 or 81, wherein the composition is formulated as a liquid, powder, suspension, paste, pellet, or gel.
83. The composition of any one of claims 80-82, wherein the insecticide is present in an amount ranging from 0.001 to 10,000 ppm, 0.1 to 2000 ppm, or 1 to 1000 ppm.
84. A method of treating a plant comprising contacting the plant with an effective amount of the conjugate of any one of claims 1-79 or composition of any one of claims 80-83.
85. The method of claim 84, wherein the plant is suffering from a pest infestation.
86. The method of claim 85, wherein the pest infestation is an insect infestation, a nematode infestation, an arachnid infestation, or a combination thereof.
87. The method of claim 84 or 85, wherein the pest infestation is an insect infestation.
88. A method of pest control of a plant comprising contacting the plant with an effective amount of the conjugate of any one of claims 1-79 or composition of any one of claims SO- 84.
89. The method of claim 88, wherein the pest is an insect, an arachnid, a nematode, or a combination thereof.
90. The method of any one of claims 84-89, wherein the insect is from the order Lepidoptera.
91. The method of any one of claims 84-89, wherein the insect is Helicoverpa spp., Heliothis virescens, Lobesia botrana, Ostrinia nubilalis, Plutella xylostella, Pseudophisia includens, Scirpophaga incertulas, Spodoptera spp., Trichophisia ni, Tuta absoluta, Cnaphalocrocis medialis, Cydia pomonella, Chilo suppressalis, Anticarsia gemmatalis, Agrotis ipsilon, Chrysodeixis includens, or a combination thereof.
92. The method of any one of claims 84-89, wherein the insect is from the order Hemiptera.
93. The method of any one of claims 84-89, wherein the insect is selected from Lyguss spp.
94. The method of any one of claims 84-89, wherein the insect is a stink bug.
95. The method of any one of claims 84-89, wherein the insect is Euschistus spp.,
Halyomorpha halys, Nezara viridula, Piezodorus guildinii, Dichelops furcatus, or a combination thereof.
96. The method of any one of claims 84-89, wherein the insect is a thrip.
97. The method of any one of claims 84-89, wherein the insect is Frankliniella spp., Thrips spp., Dichromothrips corbettii, or a combination thereof.
98. The method of any one of claims 84-89, wherein the insect is an aphid.
99. The method of any one of claims 84-89, wherein the insect is Acyrthosiphon pisum, Aphis spp., Myzus persiccie, Rhopalosiphum spp., Schizaphis graminum, Megoura viciae, or a combination thereof.
100. The method of any one of claims 84-89, wherein the insect is a whitefly.
101. The method of any one of claims 84-89, wherein the insect is Trialeurodes vaporariorum,
Bemisia spp., or a combination thereof.
102. The method of any one of claims 84-89, wherein the insect is from the order Coleoptera.
103. The method of any one of claims 84-89, wherein the insect is Phyllotreta spp., Melanotus spp., Me H et he s aeneus, Leptinotarsa decimlineata, Ceutorhynchus spp., Diabrotica spp., Anthonomus grandis, Atomaria linearia, Agriotes spp., Epilachna spp., or a combination thereof.
104. The method of any one of claims 84-89, wherein the insect is a fly.
105. The method of any one of claims 84-89, wherein the insect is Delia spp., Ceratitis capitate, Bactrocera spp., Liriomyza spp., or a combination thereof
106. The method of any one of claims 84-89, wherein the insect is from the order Coccoidea.
107. The method of any one of claims 84-89, wherein the insect is Aonidiella aurantia, Ferrisia virgate, or a combination thereof.
108. The method of any one of claims 84-89, wherein the pest is from the order Arachnida.
109. The method of any one of claims 84-89, wherein the pest is Penthaleus major, Tetranychus spp., or a combination thereof.
110. The method of any one of claims 84-89, wherein the pest is a nematode.
111. The method of any one of claims 84-89, wherein the pest is Heterodera glycines,
Meloidogyne sp., Pratylenchus spp., Caenorhabditis elegans, or a combination thereof.
112. The method of any one of claims 84-89, wherein the pest is a member of the Pentatomidae family.
113. The method of any one of claims 84-112, wherein the pest infestation is on a leaf, stem, root, or a combination thereof.
114. The method of any one of claims 84-113, wherein the insecticide enters through the insect tarsi, optionally tarsal pores.
115. The method of any one of claims 84-114, wherein the insecticide does not significantly penetrate the cuticle of the plant.
116. The method of any one of claims 84-115, wherein the pesticide, optionally insecticide, enters through the insect tarsi, optionally tarsal pores.
117. The method of any one of claims 84-116, wherein the pesticide, optionally insecticide, does not significantly penetrate the cuticle of the plant.
PCT/US2024/057643 2023-11-29 2024-11-27 Insecticide delivery by nanocarriers Pending WO2025117659A1 (en)

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