WO2007140510A1 - Composition agrochimique comprenant des particules de cristaux liquides - Google Patents

Composition agrochimique comprenant des particules de cristaux liquides Download PDF

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WO2007140510A1
WO2007140510A1 PCT/AU2007/000756 AU2007000756W WO2007140510A1 WO 2007140510 A1 WO2007140510 A1 WO 2007140510A1 AU 2007000756 W AU2007000756 W AU 2007000756W WO 2007140510 A1 WO2007140510 A1 WO 2007140510A1
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Prior art keywords
delivery system
phytantriol
liquid crystal
cubosome
stabiliser
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Yao Da Dong
Benjamin James Boyd
Ian Larson
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Monash University
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Monash University
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    • 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
    • A01N25/02—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 containing liquids as carriers, diluents or solvents
    • 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
    • A01N25/08—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 containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • 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
    • A01N25/22—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 containing ingredients stabilising the active ingredients
    • 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
    • A01N25/24—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 containing ingredients to enhance the sticking of the active ingredients
    • 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
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group

Definitions

  • the present invention relates to an agrochemical composition comprising an agrochemical active and a delivery system. More particularly it relates to an agrochemical composition wherein the delivery system comprises cubosome liquid crystal particles comprising phytantriol and a stabiliser, the delivery system exhibiting hitherto unexpected and advantageous characteristics as compared with similar delivery systems of the prior art.
  • surfactants which enhance the absorption of the agricultural active.
  • these surfactants often have the disadvantages that their toxicity is relatively high, they have a propensity to damage the plants' outer protective layer, they tend to wash off plants when it rains, and they are often environmentally unfriendly.
  • Efforts have been made to overcome these problems by using surfactants based on polar lipids because they have comparatively lower toxicity and a resistance to 'washing off caused by rain. They can also form liquid crystals which are not destroyed by dilution.
  • International patent application PCT/AU2004/001181 discloses a composition for delivering an active agent to a biological system, the composition including a lyotropic phase that modifies release of the active.
  • the lyotropic phase includes amphiphilic surfactants having a head group formed by a charged or uncharged hydrophilic polar region and a non-polar hydrophobic tail.
  • the head group can be chosen from a wide range of structures.
  • aqueous surfactant and polar lipid phases water associates with the hydrophilic head group of the surfactant molecule (to form a 'hydrophilic domain') rather than the hydrophobic tail (the 'hydrophobic domain').
  • surfactant molecules When surfactant molecules are placed in water they self-assemble to form geometric structures, the nature of which is dictated by the interplay between local and global constraints. For example, they may form two-dimensional lamellar structures, or hexagonal liquid crystal structures, or three-dimensional bicontinuous cubic structures. It is also known that they may convert between different phases in response to various factors including changes in temperature and dilution.
  • these structures may convert between inverse micelles (L 2 ), inverse hexagonal phase (Hn), inverse cubic phase (Qn), lamellar phase (L ⁇ ), normal cubic phase (Q 1 ), normal hexagonal phase (Hi) and micelles (Li).
  • these structures may only swell to a finite dilution enabling the dispersion of the liquid crystal into particles in excess water.
  • lamellar, hexagonal and cubic phase these particles have been termed liposomes, hexosomes and cubosomes respectively. Structures of this type are disclosed for example, in US patent 5,531,925 (Landh et al).
  • GMO glycerol monooleate
  • Dispersed systems of bulk liquid crystals are unstable without the addition of a stabilizer.
  • GMO based lipids are often combined with the stabilizer known as Pluronic F 127 (depicted below) to provide stable dispersions: unlike emulsions, these liquid crystal materials are not yet used in agricultural applications.
  • F 127 inhibits fusion of individual liquid crystal particles by providing a steric barrier. It would be expected that F 127 would play a significant role in the adsorption of agricultural actives onto various surfaces such as leaves, and consequently influence the delivery of agrochemicals into the target plant.
  • the mode of interaction of F 127 with GMO is known - the hydrophobic portion is 'dissolved' into the lipid region of the liquid crystal, while the hydrophilic chains point outwards to provide the steric barrier for inhibiting fusion of the individual liquid crystal particles.
  • Phytantriol (3,7,11,15-tetramethylhexadecane-l,2,3-triol) is a polar lipid principally known for use in cosmetics and hair-care products.
  • US patent 5,834,013 (Ribier et al) assigned to L'Oreal describes the use of phytantriol and a water soluble surface active agent acting as a stabiliser for use in a dermatological or cosmetic product.
  • Phytantriol and GMO form similar liquid crystalline structure in water hence it has hitherto been assumed that they act similarly as surfactants.
  • Phytantriol has been reported to exhibit phase behaviour very similar to GMO, in particular both form a bicontinuous cubic structure in excess water at room temperature and both form a reverse hexagonal structure in excess water at higher temperatures.
  • WO-2005/014162 discloses liquid crystal dispersions based on a range of lipids, preferably glycerol monooleate (GMO), with block copolymers.
  • the dispersions are typically non-lamellar (that is, having a normal or reversed liquid crystal phase, such as cubic or hexagonal phase) or L 3 phase or a combination thereof.
  • These dispersions are formed from compositions comprising lamellar and optionally non-lamellar particles which have been heated at an elevated temperature to improve the characteristics of the dispersion.
  • the dispersion may include both non-lamellar and lamellar particles.
  • cubosome liquid crystal particles based on phytantriol provide hitherto unexpected and exceptional advantages over other surfactants such as GMO based surfactants for agrochemical applications, and that anything that causes a change from cubic phase to hexagonal phase, or cubosomes to hexosomes, results in a loss of the advantage provided by cubosome liquid crystal particles.
  • the present invention therefore provides a delivery system suitable for agricultural applications comprising cubosome liquid crystal particles, the delivery system comprising phytantriol and a stabiliser, wherein the delivery system exhibits enhanced adsorption at an agrochemical locus. Furthermore the invention provides an agrochemical composition comprising an agrochemical active and cubosome liquid crystal particle delivery system comprising phytantriol and a stabiliser, wherein the delivery system exhibits enhanced adsorption at an agrochemical locus when compared to GMO based delivery systems of the prior art.
  • the delivery system may be further characterised in that its bulk cubic phase liquid crystalline internal structure is retained when diluted to form a dispersion.
  • cubic phase can exist in three distinctly different forms (the diamond, primitive and gyroid types), and the delivery system is characterised in that on dispersion, the cubosome particles retain the original type of cubic phase exhibited by the non-dispersed bulk cubic phase.
  • the cubosome liquid crystal particles are nano-structured particles and may have some vesicles interspersed.
  • the delivery system may be further characterised in that its bulk cubosome liquid crystalline internal structure is retained irrespective of the proportion of stabiliser that is added.
  • the stabiliser of the present invention may be chosen from any stabiliser that does not induce a change in liquid crystal structure of the delivery system from cubic phase or cubosomes.
  • the stabiliser of the present invention may be chosen from amphiphilic block copolymers having blocks selected from the group comprising polyoxyalkylenes, polyvinylpyrollidone, polyvinylacetate, polyvinylalcohol, polyesters, polyamides and/or polyalkenes.
  • Preferred amphiphilic block copolymers are poloxamers which comprise at least one block of polyoxyethylene and at least one block of polyoxypropylene.
  • Particularly preferred are the F and P-seriesTM poloxamers such as poloxamer 407 (e.g. Pluronic® F 127 from BASF) or poloxamer 188 (e.g. Pluronic® F68).
  • the locus is part of a plant, such as the leaf, stem or flower of a plant or the environment adjacent a plant, such as the air or soil.
  • the active agrochemical may be chosen from any chemical applied to plants for the purpose of agriculture or horticulture such as for example, those listed at the CAS Registry of the American Chemical Society accessible through SciFinderTM and STNTM search engines.
  • the active agrochemical is chosen from the group comprising pesticides, herbicides, fungicides, growth agents including fertilizers and hormones or combinations thereof.
  • the active agrochemical may be any substance or mixture of substances used or intended to be used for preventing, destroying, repelling, attracting, inhibiting, or controlling any insects, rodents, birds, nematodes, bacteria, fungi, weeds or other forms of plant, animal or microbial life regarded as pests.
  • Typical insecticides for use in the present invention include systemic, natural, contact, organic and inorganic such as chlorine based agents (particularly organo chlorides such as DDT, hexachlorohexane, lindane, aldrin, dieldrin), organophosphates (such as malathion, phosmet, trichlorfon), pyrethroids (such as pyrethrum, allethrin, bifenthrin, deltamethrin, permethrin, resmethrin, sumithrin, tetramethrin, tralomethrin, transfluthrin), plant toxins (such as nicotine, derris, neem and caffeine).
  • organo chlorides such as DDT, hexachlorohexane, lindane, aldrin, dieldrin
  • organophosphates such as malathion, phosmet, trichlorfon
  • pyrethroids such as pyr
  • Typical herbicides for use in the present invention include contact or systemic agents such as 2,4-dichlorophenoxyacetic acid, atrazine, clopyralid, dicamba, glyphosate, imazapyr, imazapic, linuron, metoalachlor, paraquat, picloram and triclopyr.
  • Typical fertilisers including organic species (such as urea and ureaformaldehyde), inorganic species (such as sodium nitrate, phosphates, metal salts, trace elements and limestone) and natural or synthetic substances.
  • Typical fungicides include those falling within the classes of substituted benzenes (such as chloroneb, chlorothalanil, hexachlorobenzene and pentachloronitrobenzene), thiocarbamates (such as ferbam, metam sodium, thiram and ziram), ethylene bisdithiocarbamates (such as mancozeb, nameb, nabam and zineb), thiophthalimides (such as captan, captafol and folpet), copper compounds, organomercury compounds (such as ethyl mercury, methyl mercury, phenyl mercuric acetate), organotin compounds (such as fentin, triphenyl tin), cadmium compounds and miscellaneous organics (such as benomyl, cyclohexamide, iprodione, metalaxyl, thiabendazole and triadimefon).
  • substituted benzenes such as chlor
  • Typical plant hormones include those falling within the classes of abscisic acid and its derivatives, auxins, cytokinins, ethylene and its derivatives and gibberellins.
  • the plant hormones may also include salicylic acid, jasmonates, oligosaccharins, brassinolides and small extracellular signalling peptides.
  • the delivery system of the present invention comprises between 0.01 and 20 wt% phytantriol, more typically between 0.01 and 10 wt% phytantriol in the bulk phase.
  • the lower limit for the composition is dependent on the amount of dilution applied to form the dispersion.
  • the amount of dilution will in turn depend on the nature of the agricultural active with which the delivery system is intended to be used. This is typically expressed in terms of the mass of agrichemical active required per hectare coverage.
  • the dilution factor may for example, range between 1 in 10 and 1 in 1000.
  • the delivery system of the present invention comprises phytantriol it may additionally include other lipids such as GMO or monolinolein, provided that the total amount of the other lipids does not exceed 80 wt% of the amount of phytantriol present. Compositions having up to this amount of additional lipid can still be successfully dispersed as cubosomes without a detrimental phase change.
  • other lipids such as GMO or monolinolein
  • the dispersed composition comprises 0.0001 to 20 wt% block copolymer stabiliser, more typically 0.001 to 10 wt% block copolymer in the bulk phase.
  • the composition comprises 50 to 99.999 wt % water, more typically 80 to 99.99 wt% water.
  • the delivery system of the present invention exhibits significantly better performance in terms of adsorption to a locus and delivery of an agrochemical active as compared with hexosome or hexosome/cubosome based delivery systems of the prior art, or delivery systems comprising, for example, GMO based surfactants.
  • the delivery systems are capable of increasing the delivery of an agrochemical active at a hydrophobic locus such as a leaf by enhancing the mass of liquid crystal particles adsorbed to the hydrophobic surface.
  • the amount of cubosomes adsorbed to the locus is >44 mg m "2 more preferably >54 mg m "2 at a concentration of 0.3 mg of phytantriol per milligram of cubosome liquid crystal particle delivery system
  • Delivery systems in agrochemical system typically work by reducing the interfacial tension between the waxy coating on the surface of a plant leaf or stem, and the aqueous phase of the agrochemical system in which the active is dissolved.
  • Some of the delivery systems of the prior art include adjuvants designed to at least partly strip the waxy coating off the surface of the plant leaf or stem, which enhances delivery of the active but is potentially deleterious to the plant in the long term.
  • the enhanced adsorption provided by the delivery system of the present invention does not strip off the waxy coating from a locus yet provides enhanced absorption of the agrochemical active at the locus as compared with GMO based delivery systems of the prior art.
  • a delivery system of the present invention having 0.3 mg/ml of phytantriol provides >15%, more preferably >30% greater adsorption of liquid crystals to a locus than an equivalent delivery system comprising 0.3 mg/ml of GMO alone.
  • a stabilizer molecule interacts with a phytantriol particle by merely adsorbing onto the surface of the particle and can be readily detached from the surface permitting direct and intimate interaction between the surface of the particle and the surface at a locus.
  • the present invention provides a method for manufacturing a cubosome liquid crystal particle system which is suitable for delivery of an active agrochemical to a locus, the method comprising the steps of:
  • the dispersion retains the bulk cubosome liquid crystalline internal structure of the bulk phase and provides enhanced delivery of the active agrochemical at the locus.
  • the cubosome liquid crystal particles may be formed by direct dispersion of a solution of active agent and stabilizer in molten lipid into a hydrophilic solvent such as water.
  • the bulk phase of the delivery system of the present invention is prepared by adding a suitable amount of a mixture of water and stabiliser to phytantriol immediately prior to dispersion by a method chosen from ultrasonication in pulse mode, vortex mixing, centrifugation or high-pressure homogenization or combinations thereof.
  • the bulk phase may be prepared by combinations of heating, vortex mixing and centrifugation.
  • the bulk phase may be left for a week or more to allow for equilibration between the lipid, dispersant and water.
  • the dispersion is typically prepared by diluting the bulk phase followed by ultrasonication or other dispersive technique known in the art.
  • the dispersion is best stored at ambient temperature for at least two days prior to usage to enable any equilibration between lipid, dispersant and water to take place.
  • the bulk phase may be diluted by the manufacturer or diluted/further diluted by the end user, such as a farmer or horticulturalist.
  • the dilution factor will depend on a number of features including the nature of the plants, the nature of the active and the amount of active to be delivered per plant or per unit area. At one extreme the bulk phase can be diluted to almost 'infinite' dilution.
  • Phytantriol was purchased from Roche (Grenzach-Wyhlen, Germany) with nominal purity of >96.6% purity(GC Assay from certificate of analysis no. 01444062).
  • Vitamin E acetate was purchased from Sigma Aldrich Chemie (Steinhiem, Germany).
  • Myverol 18-99K was donated by Kerry Bio-Science (Norwich, NY). The major components in Myverol 18-99K are GMO (60.9 %) and glyceryl monolinoleate (21.0 %).
  • Pluronic ® F- 127 was from BASF (New Jersey, USA). These chemicals were used without further purification. Water was MiHiQ grade purified through a Millipore system (Sydney, Australia). Glass capillaries for SAXS examples were purchased from Charles Supper (Natick, MA).
  • FTIR Fourier Transform InfraRed
  • ATR Attenuated Total Reflectance
  • Liquid crystal dispersions were placed in the sample cell of the ATR attachment (horizontal ATR accessory, Pike Technologies, Madison, WI, USA ) and infrared spectra recorded as a function of time for 100 minutes with water subtraction on an Excalibur FTS 3500GX spectrometer (Bio-Rad Laboratories, Cambridge, MA, USA).
  • Spectra were determined by co-addition of 32 scans at a resolution of 4.0 cm “1 ; the detection limit was less than 0.005 absorbance units. Liquid crystal particle adsorption was monitored from the absorption peak height, which provides information on adsorbed quantity. Liquid crystal particle adsorption studies were performed as a function of dispersant concentration, liquid crystal material (GMO vs. phytantriol) and the surface chemistry of the reflection element (ZnSe vs. Tristearin). Given that the foliar is covered with waxy materials, the ZnSe ATR crystal was coated with a thin film of tristearin in order to mimic the biological surface with the advantage of being a reproducible surface.
  • GMO vs. phytantriol liquid crystal material
  • ZnSe vs. Tristearin the surface chemistry of the reflection element
  • the tristearin film was prepared by evaporation of solvent from a chloroform-based solution.
  • Figure 1 illustrates the favourable adsorption of phytantriol onto tristearin surface compared to the same dispersion onto the hydrophilic ZnSe surface.
  • the liquid crystal particle surface concentration was ascertained by comparing the absorbance due to C-H stretching against a calibration curve constructed for the liquid crystal particle components ( Figure 2). That is, over a range of concentrations the liquid crystal particle components were dried down from chloroform-based solutions, forming a thin film on the ATR crystal and FTIR spectra recorded. The IR absorbance intensity of the C-H band was accurately measured and correlated to the adsorbed lipids on the surface.
  • the calibration curves show excellent agreement with the Beer-Lambert Law (R 2 > 0.99) and enable surface concentrations of liquid crystal particles to be determined with a detection limit of 10 mg m "2 (absorbance: 0.005 at 2869 cm "1 ).
  • Example 2 The following Example determines phase structure using small angle x-ray scattering (SAXS), and examines phase changes with temperature and composition using crossed polarised light microscopy (CPLM) and differential scanning calorimetry (DSC).
  • SAXS small angle x-ray scattering
  • CPLM crossed polarised light microscopy
  • DSC differential scanning calorimetry
  • Dispersed systems 900 mg of lipid was weighed into a 20 mL glass vial. 10 mL of water containing F 127 (1 wt %) was added immediately prior to dispersion by ultrasonication (Misonix XL2000, Misonix Incorporated, Farmingdale, NY) for 20 minutes in pulse mode (0.5 s pulses interrupted by 0.5 s breaks) at 40% of maximum power, resulting in a milky dispersion. Dispersions were stored at 25 0 C for at least two days prior to usage for further examples to enable any equilibration between lipid, F 127 and water to take place.
  • SAXS Small-Angle X-ray Scattering Measurements
  • Crossed Polarized Light Microscopy (CPLM). Cross polarised light microscopy using a Zeiss Axiolab E microscope fitted with crossed polarising filters and a magnification of 150 was used to observe the texture of the bulk mesophases. The textures were compared to those reported by Rosevear (1968) in order to assign the appropriate mesophases. A small amount of the bulk phase was placed on a microscope slide beneath a cover slip, and in order to minimize the effect of water loss during heating, the bulk phase was flooded with excess water. The sample was heated from room temperature to 80 °C at a rate of 1 0 C per minute using a Linkam HFS 91 heating stage) and a TP-93 temperature programmer (Linkam, Surrey, England).
  • DSC Differential Scanning Calorimetry
  • Phytantriol based dispersions containing 9 % w/w and 1% F 127 were metastable for several months when stored at 25 0 C. Some aggregation of lipid at the water/air interface was apparent, but was easily redispersed with hand shaking.
  • SAXS data taken 2 weeks after preparation revealed that the space group was Pn3m, same as that displayed by the bulk phase, and that the lattice parameter was essentially identical at 68.6 ⁇ 0.3 A compared to 68.2 ⁇ 0.4 A for the bulk phase.
  • the change in space group for GMO bulk phase on addition of F 127 from Pn3m to Im3m was also observed on dispersion.
  • the phase structure of the GMO-based dispersion was identical to the equivalent bulk phases containing F 127, with a space group of Im3m, and a lattice parameter of 129.7 ⁇ 0.8 A (see Table 1).
  • GMO-based dispersions were visually more stable than the phytantriol-based system. There was minimal aggregation of particles upon extended storage being evident compared to the phytantriol dispersions.
  • Example 1 The sample preparation, method validation and method of measurement were the same as for Example 1.
  • liquid crystal particle adsorption studies were performed as a function of dispersant concentration, phase (cubosomes vs. hexosomes), liquid crystal material (GMO vs phytantriol) and the surface chemistry of the reflection element (ZnSe vs Tristearin).
  • Hexosomes in all examples contained vitamin E acetate in phytantriol at a ratio of 1 :9.
  • the ZnSe ATR crystal was coated with a thin film of tristearin in order to mimic the biological surface.
  • the tristearin film was prepared by drying down from a chloroform-based solution.
  • Figure 4 comprises a graph depicting the amount of liquid crystal particles adsorbed on surfaces after 100 minutes using liquid crystal dispersions at a concentration of 0.3 mg/ml and F127 0.033 mg/ml.
  • the graph demonstrates differences in adsorption of the particles to the uncoated (ZnSe) and wax-coated (tristearin) surface, and that the adsorption decreases in the order Phytantriol cubosomes>Myverol cubosomes>hexosomes. Specifically, it depicts the superior adsorption of cubosome liquid particles made from phytantriol, as compared with those made from Myverol, or hexosome liquid particles. The graph also shows that the cubosome liquid particles made from phytantriol have a greater preference for the hydrophobic surface over the other systems when compared to the hydrophilic ZnSe
  • Example 4 illustrates the adsorption of a compound incorporated into the particle system of the present invention to a surface mimicking a leaf (tristearin coated glass slide) and the quantity of material retained on the surface after extensive rinsing with water.
  • the glass slides were placed vertically in a 25 ml beaker and fully immersed in the liquid of interest (liquid crystal dispersions or control solutions containing the radiolabeled probe molecules) for 3 hours.
  • the slides are then removed from the dispersion and dipped sequentially in 5 beakers of 20ml of fresh water to rinse off any excess particles to ensure that only absorbed particles remained on the tristearin surface.
  • the rinsing solutions were collected and analysed for radioactivity to confirm that the final rinse was not removing significant radioactive material from the surface as a confirmation of the rinsing process.
  • the slides were then immersed in 3 ml of Solvate for 1 hour in room temperature to remove the tristearin layer and adhered particles into solution.
  • the Solvate solution was added to Starscint scintillation cocktail and the slides were rinsed repeatedly with StarScint to ensure complete removal and collection of all radioactivity from the slides.
  • Adsorption to uncoated slides was measured in an identical fashion to allow subtraction of adsorption from the uncoated side of the slide in the tristearin adsorption experiment.
  • Figure 5 is a graph illustrating the amount of radiolabel remaining on the slide after rinsing five times by immersion in fresh water.
  • the graph shows that the efficacy of delivery of an active to a hydrophobic leaf-like surface depends on the choice of liquid crystal structure of the particle. Again the efficacy decreases in the order, phytantriol cubosomes (nearly twice as effective) >Myverol cubosomes>hexosomes. This is in agreement with the FTIR result in Example 3, and implies that the particles and the agent are being delivered to the surface together and adhere under rinsing conditions.
  • This example illustrates the interaction of lipids with a waxy surface such as the surface of a leaf. More particularly it illustrates the beneficial but different interaction between the waxy layer and the liquid crystal particles, in terms of disruption of the waxy layer structure to assist an active to penetrate the leaf once delivered to the surface.
  • the positive control is a commercial agricultural adjuvant (Input ® penetrant (DuPont Australia) and the negative control is water.
  • the 'F 127 stabilizer only' formulation includes Pluronic ® F127 stabilizer without the lipid present, i.e. just the stabilizing polymer.
  • the other three formulations are those described above in examples 3 and 4. Radiolabeled 3 H diazepam was incorporated into the film, and the ability of the particles to disrupt the waxy layer was determined by release of diazepam into the solution over time.
  • Figure 6 is a graph depicting the release of diazepam from the film on exposure to formulations.
  • the commercial agricultural adjuvant performed best because it is designed to strip off the waxy layer, often with a deleterious effect on the plant.
  • the cubosome liquid crystal formulation from phytantriol provided excellent release of diazepam by disrupting the waxy layer, but would not strip off the waxy layer as the commercial agricultural adjuvant does.
  • Lipid bases were prepared by mixing phytantriol and GMO (Myverol 18-99K) at 60 0 C for 10 min, then at 37 0 C overnight; 250 mg of each mixture was accurately weighed into a 12 mL polypropylene tube. A 1% Pluronic F 127 solution in water was then prepared, and 4.75 mL added to each polypropylene tube and the tube immediately vortexed and sonicated in a sonicating bath for 10 min to obtain a coarse dispersion. The coarse dispersion was then refined using a Misonix tip ultrasonicator at Power setting 4 for 5 min, 0.5s on/off pulses.
  • GMO Myverol 18-99K
  • the patterns were indexed to known space groups, and the lattice parameter calculated for each composition.
  • FIG. 7 is a graph showing lattice parameter (A) and space group data calculated from I vs q plots for Phytantriol/Myverol 18-99K cubosomes.
  • the Pn3m phase indicates no interaction between the cubosomes structure and the polymer, and hence will likely give better adsorption at all of the compositions for which the Pn3m phase exists.
  • FIG. 8 shows the amount of tritium (DPM) associated with different forms of microparticles adhering to a tristearin layer after 3 hours. Specifically it demonstrates delivery of the herbicide to the surface changes with changes in liquid crystal structure (formulation composition). The compositions and procedures were identical to Example 6 except that the herbicide (DDE) has been substituted for diazepam.
  • DPM tritium
  • DDE radioactive herbicide
  • Examples 9 and 10 below show the effect of composition on the ability of the herbicide (DDE) to remain on the surface after the composition is dried on the surface and then re-immersed in water.
  • This experiment is designed to mimic 'in use' conditions in which the formulation is applied to the surface (plant) and at some time later the leaf is exposed to rain. The amount removed is as a percentage of the total applied.
  • the DuPont input penetrant removes wax from the surface taking DDE with it, while PHYT cubosomes perform best as they stick well to the surface, and do not come off on rinsing.
  • Figure 10 is a graph of the (%) amount of DDE removed from the tristearin covered glass slip after 3 hours immersion in water at room temperature and agitated on a shaker at 50 rpm.
  • Figure 1 is a graph of the adsorption (mg/m 2 ) against time (mins) of cubosomes on
  • Figure 2 is a calibration curve of infra red absorbance at 2869 cm “1 as a function of mass of phytantriol applied to the ZnSe surface (mg/m 2 ) at increasing concentrations, showing the linear response for absorption of IR signal;
  • Figure 3 is a graph of Intensity (A.U) against wavelength (A) for phytantriol dispersions (9 % w/w in water) containing increasing concentration of F 127.
  • concentrations of F 127 in phytantriol are (a) 11% w/w, (b) 22 % w/w, and (c) 33 % w/w at 25 °C;
  • Figure 4 is a graph of the amount of liquid crystal particles (mg m "2 ) adsorbed on a
  • Figure 5 is a graph of radioactivity remaining on a tristearin surface after immersion for 3 hours in a cubosome/hexosome dispersion solution (having a concentration of 7.5 mg/ml) following 5 washings in water;
  • Figure 6 is a graph of the percentage radioactively labelled diazepam released over time (mins) from film exposed to various carrier systems.
  • Figure 7 is a graph showing lattice parameter (A) and space group data calculated from I vs q plots for Phytantriol/Myverol 18-99K cubosomes.
  • DPM radioactive herbicide
  • DDE radioactive herbicide
  • Figure 10 is a graph of the (%) amount of DDE removed from a tristearin covered glass slip after 3 hours immersion in water at room temperature and agitated on a shaker at 50 rpm.
  • Figure 11 is a graph of the (%) amount of DDE removed from the Hebe plant leaves after 3 hours immersion in water.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne un système d'alimentation pour des applications agricoles comprenant des particules de cristaux liquides de forme cubique, le système d'alimentation comprenant le phytantriol et un agent stabilisant, le système d'alimentation présentant une meilleure adsorption au niveau d'un site agrochimique.
PCT/AU2007/000756 2006-06-02 2007-05-30 Composition agrochimique comprenant des particules de cristaux liquides Ceased WO2007140510A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2566322A4 (fr) * 2010-05-06 2013-12-11 Basf Se Dispersion à effet pesticide comprenant une phase dispersée nanostructurée
WO2022087686A1 (fr) * 2020-10-30 2022-05-05 Royal Melbourne Institute Of Technology Particule à phase cristalline liquide lyotrope
WO2024153171A1 (fr) * 2023-01-19 2024-07-25 石河子大学 Émulsion de pesticide ayant une structure de cristaux liquides, son procédé de préparation et son utilisation

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2566322A4 (fr) * 2010-05-06 2013-12-11 Basf Se Dispersion à effet pesticide comprenant une phase dispersée nanostructurée
WO2022087686A1 (fr) * 2020-10-30 2022-05-05 Royal Melbourne Institute Of Technology Particule à phase cristalline liquide lyotrope
WO2024153171A1 (fr) * 2023-01-19 2024-07-25 石河子大学 Émulsion de pesticide ayant une structure de cristaux liquides, son procédé de préparation et son utilisation

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