US20090239749A1 - Biocidal compositions - Google Patents

Biocidal compositions Download PDF

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US20090239749A1
US20090239749A1 US12/309,293 US30929307A US2009239749A1 US 20090239749 A1 US20090239749 A1 US 20090239749A1 US 30929307 A US30929307 A US 30929307A US 2009239749 A1 US2009239749 A1 US 2009239749A1
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water
biocide
dispersion
insoluble
nano
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David John Duncalf
Alison Jayne Foster
James Long
Steven Paul Rannard
Dong Wang
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Iota Nanosolutions Ltd
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Conopco Inc
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Assigned to CONOPCO, INC. D/B/A UNILEVER reassignment CONOPCO, INC. D/B/A UNILEVER ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DUNCALF, DAVID JOHN, FOSTER, ALISON JAYNE, LONG, JAMES, RANNARD, STEVEN PAUL, WANG, DONG
Publication of US20090239749A1 publication Critical patent/US20090239749A1/en
Assigned to IOTA NANOSOLUTIONS LIMITED reassignment IOTA NANOSOLUTIONS LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CONOPCO, INC. D/B/A UNILEVER
Assigned to IOTA NANOSOLUTIONS LIMITED reassignment IOTA NANOSOLUTIONS LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CONOPCO, INC. D/B/A UNILEVER
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    • A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
    • A61K9/1605—Excipients; Inactive ingredients
    • A61K9/1617—Organic compounds, e.g. phospholipids, fats
    • 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
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Definitions

  • the present invention concerns improvements relating to biocidal compositions.
  • biocidal compositions and precursors thereof which contains a water-insoluble biocidal substance.
  • Biocidal agents are widely used in agriculture, sanitation and cleaning, wood and paper preservation and various other human, animal and plant health and industrial applications.
  • the present invention is believed to be generally applicable to biocidal compositions but will be described with particular reference to antimicrobial agents, i.e. anti-bacterial and anti-fungal agents and also herbicides, although other and broader aspects of the invention are not intended to be excluded.
  • WO 2005/011636 discloses a non-emulsion based spray drying process for forming ‘solid amorphous dispersions’ of drugs in polymers.
  • a polymer and a low-solubility drug are dissolved in a solvent and spray-dried to form dispersions in which the drug is mostly present in an amorphous form rather than in a crystalline form.
  • GB 0613925 the water-insoluble materials are dissolved in a mixed solvent system and co-exist in the same phase as a water-soluble structuring agent.
  • Our GB 0613925 application makes it clear that a TriclosanTM nano-dispersion has the additional benefit that weight for weight it is more effective than is normally expected of TriclosanTM even at very low concentrations.
  • ambient temperature means 20 degrees Celsius and all percentages are percentages by weight unless otherwise specified.
  • a first aspect of the present invention provides a biocidal preparation of improved efficacy comprising at least one water insoluble biocide and a water-soluble carrier material, wherein the water-insoluble biocide is dispersed through the carrier material in nano-disperse form having a peak diameter of the nano-disperse form below 1000 nm.
  • the present invention further provides a process for improving the efficacy of a water insoluble biocide which comprises the step of spray drying a solution of the biocide and a solution of a water-soluble carrier to obtain a solvent free dispersion of the biocide in the carrier, which, when dissolved in water produces a nano-disperse biocide with a peak particle diameter of below 1000 nm.
  • the preferred method of particle sizing for the dispersed products of the present invention employs a dynamic light scattering instrument (Nano S, manufactured by Malvern Instruments UK). Specifically, the Malvern Instruments Nano S uses a red (633 nm) 4 mW Helium-Neon laser to illuminate a standard optical quality UV curvette containing a suspension of material. The particle sizes quoted in this application are those obtained with that apparatus using the standard protocol.
  • the peak diameter of the water-insoluble biocide is below 800 nm. More preferably the peak diameter of the water-insoluble biocide is below 500 nm. In a particularly preferred embodiment of the invention the peak diameter of the water-insoluble biocide is below 200 nm, most preferably below 100 nm.
  • water insoluble as applied to the biocide means that its solubility in water is less than 10 g/L.
  • the water insoluble biocide has solubility in water at ambient temperature (20 Celsius) of less than 5 g/L preferably of less than 1 g/L, especially preferably less than 120 mg/L, even more preferably less than 15 mg/L and most preferably less than 5 mg/L.
  • This solubility level provides the intended interpretation of what is meant by water-insoluble in the present specification.
  • the present invention is applicable to a broad range of biocides.
  • Preferred water-insoluble biocides for use in the present invention are antibacterials (for example chlorophenols including Triclosan), antifungals (for example organochlorines including Chlorothalonil and imidazoles such as Ketoconazole and Propiconazole), insecticides (for example pyrethroids, including ⁇ -cyhalothrin) and/or herbicides (for example phenol-ureas including Isoproturon).
  • the invention is also envisaged to be applicable to acaricides, algicides, molluscicides and nematacides.
  • Triclosan (5-chloro-2-(2,4-dichlorophenoxy)-phenol) is an chlorophenol antibacterial used in soaps, deodorants, toothpastes, mouthwashes, and cleaning supplies and is infused in an increasing number of consumer products, such as kitchen utensils, toys, bedding, socks, and trash bags. It has a poor solubility in water of 17 mg/L and is a suitable antibacterial biocide for use in the present invention.
  • Ketoconazole acetyl-dichlorophenyl-imidazole
  • Creams, lotions and medicated shampoos are available for topical infections such as dandruff, whilst an oral tablet is used to treat systemic fungal infections.
  • Janssen-Cilag Ltd produce a variety of ketoconazole based formulations under the trade name “Nizoral®”. It has a solubility of less than 0.1 mg/L.
  • Propiconazole (1-(2-(2,4-dichlorophenyl)-4-propyl-1-1,3-dioxolan-2-ylmethyl)-1H-1,2,4-tri azole) is another broad spectrum antifungal agent. Propiconazole is predominantly used in antifungal agrochemical formulations such as “Tilt®” manufactured by Ciba. It has a solubility of around 100 mg/L.
  • Azoxystrobin (methyl(E)-2- ⁇ 2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl ⁇ -3-methoxyacrylate) is a systemic, broad-spectrum strobilurin fungicide with activity against the four major groups of plant pathogenic fungi including Ascomcetes (e.g. powdery mildews), Basidiomycetes (e.g. rusts), Deutoromycetes (e.g. rice blast) and Oomycetes (e.g. downy mildew).
  • Ascomcetes e.g. powdery mildews
  • Basidiomycetes e.g. rusts
  • Deutoromycetes e.g. rice blast
  • Oomycetes e.g. downy mildew
  • strobilurins are azoxystrobin, kresoxim-methyl, picoxystrobin, fluoxastrobin, oryzastrobin, dimoxystrobin, pyraclostrobin and trifloxystrobin.
  • Azoxystrobin has a very poor solubility in water of ⁇ 6 mg/L
  • Chlorothalonil (2,4,5,6-tetrachloroisophthalonitrile) is a broad-spectrum organo-chlorine fungicide used to control fungi that threaten vegetables, trees, small fruits, turf, ornamentals, and other agricultural crops. It has an exceptionally low solubility in water of ⁇ 0.6 mg/L.
  • Ketoconazole, propiconazole, azoxystrobin and chlorothalonil are each suitable antifungal biocides for use in the present invention.
  • Isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) is a common herbicide with a low solubility in water ( ⁇ 65 mg/L) and is widely used for the control of broad leaved weeds that grow in various annual grasses. It is a suitable herbicide for use in the present invention.
  • ⁇ -cyhalothrin is a suitable insecticide for use in the present invention and has an aqueous solubility of 0.005 mg/L
  • Preferred carrier materials are selected from the group consisting of water-soluble inorganic materials, surfactants, polymers, sugars and mixtures thereof.
  • a further aspect of the present invention provides an aqueous dispersion of a water insoluble biocide and a water-soluble carrier material, wherein the biocide is in nano-disperse form having a peak diameter of the nano-disperse form below 1000 nm, preferably below 800 nm, more preferably below 500 nm, even more preferably below 200 nm and especially below 100 nm. As noted above, it is particularly advantageous when the particle size of the biocide is below 40 nm.
  • a further aspect of the present invention provides a method for preparing a biocide composition comprising a water insoluble biocide and a water-soluble carrier, which comprises the steps of:
  • this class of method is referred to herein as the “emulsion” method.
  • a further aspect of the present invention provides a method for preparing a biocide composition comprising a water insoluble biocide and a water-soluble carrier which comprises the steps of:
  • this class of method is referred to herein as the “single-phase” method.
  • substantially solvent free means that the free solvent content of the product is less than 15% wt, preferably below 10% wt and more preferably below 5% wt.
  • both the carrier material and the biocide are essentially fully dissolved in their respective solvents prior to the drying step. It is not within the ambit of the present specification to teach the drying of slurries. For the avoidance of any doubt, it is therefore the case that the solids content of the emulsion or the mixture is such that over 90% wt, preferably over 95%, and more preferably over 98% of the soluble materials present is in solution prior to the drying step.
  • the preferred biocide and the preferred carrier materials are as described above and as elaborated on in further detail below.
  • the “single phase” method where both the biocide and the carrier material are dissolved in a phase comprising at least one non-aqueous solvent (and optional water) is preferred. This is believed to give a smaller particle size for the nano-disperse biocide.
  • drying simultaneously removes essentially all solvents and, more preferably, is accomplished by spray drying at above ambient temperature.
  • a further aspect of the present invention provides a method for the preparation of a biocide composition for use in the prophylaxis or treatment of infections or infestations which comprises the step of preparing a composition according to the present invention.
  • the method is one in which the particle size of the water-insoluble biocide is reduced to below 100 nm, more preferably below 40 nm.
  • Such compositions are suitable for use in methods of medical treatment.
  • a still further aspect of the present invention provides for the treatment of a substrate other than a medical treatment which comprises the step of contacting the substrate with a composition according to the present invention.
  • a method might comprise, for example, a method for preserving wood or other materials of natural origin.
  • biocides are non-animal biocides, particularly fungicides, bactericides and herbicides.
  • these biocides have solubility in water of less than 120 mg/L and more preferably less than 15 mg/L.
  • biocide also includes biostats.
  • propiconazole is “fungistatic” rather than “fungicidal” as its mode of action involves inhibition of cell mitosis, rather than causing cell death.
  • Some known water-insoluble herbicides are listed in U.S. Pat. No. 6,849,577 and include diuron, linuron, sulfometuron, chlorsulphuron, metsulfuron, chlorimuron, atrazine, simazine, quizalofop, butroxydim, nicosulfuron, primsulfuron, bensulfuron, ametryn, pendimethalin, isoproturon, chlortoluron, diflufenican, mesotrione, aclonifen, fluorochloridone, oxyfluorfen, isoxaflutole, imazamox and thifensulfuron.
  • herbicides include trifluralin, fluoroxypyr, phenmedipham, fenoxaprop-P-ethyl, acetochlor, alachlor, tri-allate and propanil.
  • the present invention does not depend critically on the nature of the water-insoluble herbicide.
  • the invention is suitable for application with the insoluble form of those herbicides, as mentioned above, which are currently used in salt form.
  • those herbicides include glyphosphate (N-phosphonomethylglycine), which is commonly used in the form of its water-soluble salts such as trimethylsulphonium, isopropylamine, sodium, or ammonium salts, fomesafen which is commonly used in the form of its water-soluble sodium salt, glufosinate which is commonly used in the form of its water-soluble ammonium salt, paraquat dichloride and bentazone which is commonly used in the form of its water-soluble sodium salt.
  • glyphosphate N-phosphonomethylglycine
  • water-soluble salts such as trimethylsulphonium, isopropylamine, sodium, or ammonium salts
  • fomesafen which is commonly used in the form of its water-soluble sodium salt
  • glufosinate
  • Some known water-insoluble fungicides are disclosed in, for example, U.S. Pat. Nos. 6,355,675 and 6,113,936 and include benzimidazole compounds such as benomyl, carbendazim, thiabendazole and thiophanate-methyl; phenylcarbamate compounds such as diethofencarb; dicarboxyimide compounds such as procymidone, iprodione and vinclozolin; azole compounds such as diniconazole, epoxyconazole, tebuconazole, difenoconazole, cyproconazole, flusilazole, flutriafol and triadimefon; acylalanine compounds such as metalaxyl; carboxyamide compounds such as furametpyr, mepronil, flutolanil and tolyfluanid; organophosphate compounds such as tolclofos-methyl, fosetyl aluminum and pyrazophos; anilinopyrim
  • Preferred fungicides include those of the polyene, imidazole and triazole types.
  • Particular preferred polyenes include Amphotericin, Nystatin and mixtures thereof.
  • Preferred imidazoles include: Bifonazole, Butoconazole, Clotrimazole, Econazole, Fenticonazole, Isoconazole, Ketoconazole, Metronidazole, Oxiconazole, Sertaconazole, Sulconazole, Tioconazole, Miconazole and mixtures thereof.
  • Preferred triazole types include: Fluconazole, Itraconazole, Posaconazole, propiconazole, Ravuconazole, tebuconazole, Terconazole, Voriconazole and mixtures thereof.
  • antifungal biocides for use in the present invention include: Amorolfine, Anidulafungin, Butenafine, Naftifine, Caspofungin, Ciclopirox, Flucytosine, Griseofulvin, Haloprogin, Micafungin, Parabens, Salicylic acid, Terbinafine, Thiabenazole, Tolnaflate, Undecylenic acid and mixtures thereof.
  • Water insoluble insecticides include cypermethrin, lambda-cyhalothrin, esfenvalerate, malathion, and chlorpyrifos.
  • the present invention provides a method for obtaining a rapidly dispersible form of an otherwise essentially water-insoluble material. This is prepared by forming an at least partially non-aqueous intermediate emulsion or solution in which both a water-soluble carrier material and the water-insoluble biocide are dissolved. On removal of solvents the insoluble biocide is left dispersed through the water-soluble carrier material. Suitable carrier materials are described in further detail below.
  • the most preferred method for drying of the intermediate emulsion or solution is one which produces a powder directly, such as spray drying.
  • Spray drying is particularly effective at removing both the non-aqueous volatile components and any water present to leave the carrier and the ‘payload’ material behind in a powder form. The drying step is described in further detail below.
  • the structure of the material obtained after the drying step is not well understood. It is believed that the resulting dry powder materials are not encapsulates, as discrete macroscopic bodies of the water-insoluble materials are not present in the dry product. Neither are the dry materials ‘dry emulsions’ as little or none of the volatile solvent comprising the ‘oil’ phase of the emulsion remains after the drying step. On addition of water to the dry product the emulsion is not reformed, as it would be with a ‘dry emulsion’. It is also believed that the compositions are not so-called solid solutions, as with the present invention the ratios of components present can be varied without loss of the benefits. Also from Xray and DSC studies, it is believed that the compositions of the invention are not solid solutions, but comprise nano-scale, phase-separated mixtures.
  • the compositions produced after the drying step will comprise the biocide and the carrier in a weight ratio of from 1:500 to 1:1 as biocide:carrier, with 1:100 to 1:1 being preferred.
  • Typical levels of around 10-30% wt water-insoluble biocide and 90-70% carrier can be obtained by spray drying.
  • Levels of biocide below 40%, more preferably below 30% wt and most preferably below 25% wt are preferred as they show the improved MIC as discussed above.
  • the solvent for the water-insoluble biocide is not miscible with water. On admixture with water it therefore can form an emulsion.
  • the non-aqueous phase comprises from about 10% to about 95% v/v of the emulsion, more preferably from about 20% to about 68% v/v.
  • the emulsions are typically prepared under conditions which are well known to those skilled in the art, for example, by using a magnetic stirring bar, a homogeniser, or a rotational mechanical stirrer.
  • the emulsions need not be particularly stable, provided that they do not undergo extensive phase separation prior to drying.
  • Homogenisation using a high-shear mixing device is a particularly preferred way to make an emulsion in which the aqueous phase is the continuous phase. It is believed that this avoidance of coarse emulsion and reduction of the droplet size of the dispersed phase of the emulsion, results in an improved dispersion of the biocide in the dry product.
  • a water-continuous emulsion is prepared with an average dispersed-phase droplet size (using the Malvern peak intensity) of between 500 nm and 5000 nm.
  • an ‘Ultra-Turrux’T25 type laboratory homogenizer or equivalent gives a suitable emulsion when operated for more than a minute at above 10,000 rpm.
  • the re-dissolved particle size can be reduced by nearly one half when the homogenization speed increased from 13,500 rpm to 21,500 rpm.
  • the homogenization time is also believed to play a role in controlling re-dissolved particle size.
  • the particle size again decreases with increase in the homogenization time, and the particle size distribution become broader at the same time.
  • Such intensive mixing is not an essential step in the method of the present invention but it is advantageous.
  • Sonication is also a particularly preferred way of reducing the droplet size for emulsion systems.
  • a Hert Systems Sonicator XL operated at level 10 for two minutes is suitable.
  • the ‘single-phase’ method is generally believed to give a better nano-dispersion with a smaller particle size than the emulsion method. As noted above, the smaller particle sizes give enhanced biocidal effects.
  • ratios of components which decrease the relative concentration of the biocide to the solvents and/or the carrier give a smaller particle size.
  • Spray drying the most preferred method of drying the emulsion or solution, is well known to those versed in the art. In the case of the present invention some care must be taken due to the presence of a volatile non-aqueous solvent in the material being dried.
  • an inert gas for example nitrogen, can be employed as the drying medium in a so-called closed spray-drying system. The solvent can be recovered and re-used.
  • the drying temperature should be at or above 100 Celsius, preferably above 120 Celsius and most preferably above 140 Celsius. Elevated drying temperatures have been found to give smaller particles in the re-dissolved nano-disperse material.
  • Freeze drying can also be used. It is preferred to use a non-aqueous solvent with a melting point above ⁇ 120 Celsius, preferably above ⁇ 80 Celsius. Chloroform is a particularly preferred solvent due to it physical characteristics. It a relatively high melting point (approx. ⁇ 63.5° C.). Freeze drying can be employed both with the emulsion method and the single phase method.
  • the carrier material is water soluble, which includes the formation of structured aqueous phases as well as true ionic solution of molecularly mono-disperse species.
  • the carrier material preferably comprises an inorganic material, surfactant, a polymer or may be a mixture of two or more of these.
  • Suitable carrier materials include preferred water-soluble polymers, preferred water-soluble surfactants and preferred water-soluble inorganic materials. Particularly preferred materials are solids, as opposed to soft solids or semi-solids at ambient temperature such that good powder properties are obtained in the spray-dried product.
  • carrier material will depend on the proposed end-use of the composition and carriers should be selected such that they are not detrimentally reactive towards the biocide and compatible with the proposed use.
  • the carrier can also have an activity in its own right or contain water soluble materials which have such an activity.
  • the carrier may comprise materials having an agrochemical activity.
  • Suitable water-soluble polymeric carrier materials include:
  • suitable and preferred homopolymers include poly-vinylalcohol, poly-acrylic acid, poly-methacrylic acid, poly-acrylamides (such as poly-N-isopropylacrylamide), poly-methacrylamide; poly-acrylamines, poly-methyl-acrylamines, (such as polydimethylaminoethylmethacrylate and poly-N-morpholinoethylmethacrylate), polyvinylpyrrolidone, poly-styrenesulphonate, polyvinylimidazole, polyvinylpyridine, poly-2-ethyl-oxazoline poly-ethyleneimine and ethoxylated derivatives thereof.
  • Polyethylene glycol PEG
  • polyvinylpyrrolidone PVP
  • polyvinyl alcohol PVA
  • HPMC hydroxypropyl-methyl cellulose
  • alginates are preferred polymeric carrier materials.
  • the surfactant may be non-ionic, anionic, cationic, amphoteric or zwitterionic.
  • non-ionic surfactants include ethoxylated triglycerides; fatty alcohol ethoxylates; alkylphenol ethoxylates; fatty acid ethoxylates; fatty amide ethoxylates; fatty amine ethoxylates; sorbitan alkanoates; ethylated sorbitan alkanoates; alkyl ethoxylates; PluronicsTM; alkyl polyglucosides; stearol ethoxylates; alkyl polyglycosides.
  • anionic surfactants include alkylether sulfates; alkylether carboxylates; alkylbenzene sulfonates; alkylether phosphates; dialkyl sulfosuccinates; sarcosinates; alkyl sulfonates; soaps; alkyl sulfates; alkyl carboxylates; alkyl phosphates; paraffin sulfonates; secondary n-alkane sulfonates; alpha-olefin sulfonates; isethionate sulfonates.
  • Suitable cationic surfactants include fatty amine salts; fatty diamine salts; quaternary ammonium compounds; phosphonium surfactants; sulfonium surfactants; sulfonxonium surfactants.
  • Suitable zwitterionic surfactants include N-alkyl derivatives of amino acids (such as glycine, betaine, aminopropionic acid); imidazoline surfactants; amine oxides; amidobetaines.
  • Mixtures of surfactants may be used.
  • Alkoxyayed nonionic's (especially the PEG/PPG e.g. PluronicTM materials and/or the PEG/alcohol nonionics), phenol-ethoxylates (especially TRITONTM materials), alkyl sulphonates (especially SDS), ether-sulphates (including SLES), ester surfactants (preferably sorbitan esters of the SpanTM and TweenTM types) and cationics (especially cetyltrimethylammonium bromide—CTAB) are particularly preferred as surfactant carrier materials.
  • PEG/PPG e.g. PluronicTM materials and/or the PEG/alcohol nonionics
  • phenol-ethoxylates especially TRITONTM materials
  • alkyl sulphonates especially SDS
  • ether-sulphates including SLES
  • ester surfactants preferably sorbitan esters of the SpanTM and TweenTM types
  • cationics especially cetyltrimethylammonium bromid
  • Surfactant carrier materials are particularly suitable for embodiments of the invention in which the re-dispersed particle size in water is below 100 nm, and particularly below 40 nm.
  • Preferred mixtures include combinations of inorganic salts and surfactants and polymers and surfactants.
  • Particularly preferred mixtures include combinations of surfactants and polymers. Which include at least one of:
  • the carrier material can also be a water-soluble small organic material which is neither a surfactant, a polymer nor an inorganic carrier material.
  • Simple organic sugars have been found to be suitable, particularly in admixture with a polymeric and/or surfactant carrier material as described above.
  • Suitable small organic materials include mannitol, polydextrose, xylitol and insulin etc.
  • the level of surfactant carrier is such that at least 50% of the total carrier is surfactant. Mixtures having a majority of surfactant present over the other carriers exhibit better biocidal effects.
  • compositions of the invention comprise a volatile, non-aqueous solvent.
  • a volatile, non-aqueous solvent As noted above this can be a mixture of solvents. This may either be miscible with such other solvents (including water) which may be present in the pre-mix before drying or, together with those solvents may form an emulsion.
  • Particularly preferred solvents are selected from the group consisting of haloforms (preferably di-chloromethane, chloroform), lower (C1-C10) alcohols (preferably methanol, ethanol, isopropanol, isobutanol), organic acids (preferably formic acid, acetic acid), amides (preferably formamide, N,N-dimethylformamide), nitrites (preferably aceto-nitrile), esters (preferably ethyl acetate) aldehydes and ketones (preferably methyl ethyl ketone, acetone), and other water miscible species comprising heteroatom bond with a suitably large dipole (preferably tetrahydrofuran, dialkylsulphoxide). Mixtures of the aforementioned may also be employed.
  • haloforms preferably di-chloromethane, chloroform
  • lower (C1-C10) alcohols preferably methanol, ethanol, isopropanol, isobutanol
  • the non-aqueous solvent is not miscible with water and forms an emulsion.
  • the non-aqueous phase of the emulsion is preferably selected from one or more from the following group of volatile organic solvents:
  • Preferred solvents include dichloromethane, chloroform, ethanol, acetone and dimethyl sulphoxide.
  • Preferred non-aqueous solvents whether miscible or not have a boiling point of less than 150 Celsius and, more preferably, have a boiling point of less than 100 Celsius, so as to facilitate drying, particularly spray-drying under practical conditions and without use of specialised equipment.
  • they are non-flammable, or have a flash point above the temperatures encountered in the method of the invention.
  • Particularly preferred solvents are alcohols, particularly ethanol and halogenated solvents, more preferably chlorine-containing solvents, most preferably solvents selected from (di- or tri-chloromethane).
  • an optional co-surfactant may be employed in the composition prior to the drying step.
  • a relatively small quantity of a volatile cosurfactant reduced the particle diameter of the material produced. This can have a significant impact on particle volume. For example, reduction from 297 nm to 252 nm corresponds to a particle size reduction of approximately 40%.
  • the addition of a small quantity of co-surfactant offers a simple and inexpensive method for reducing the particle size of materials according to the present invention without changing the final product formulation.
  • Preferred co-surfactants are short chain alcohols or amine with a boiling point of ⁇ 220° C.
  • the co-surfactant is present in a quantity (by volume) less than the solvent preferably the volume ratio between the solvent and the co-surfactant falls in the range 100:40 to 100:2, more preferably 100:30 to 100:5.
  • drying feed-stocks used in the present invention are either emulsions or solutions which preferably do not contain solid matter and in particular preferably do not contain any undissolved biocide.
  • the level of the biocide in the composition should be such that the loading in the dried composition is below 40% wt, and more preferably below 30% wt.
  • Such compositions have the advantages of a small particle size and high effectiveness as discussed above.
  • Typical spray drying feedstocks comprise:
  • the particle size of the water-insoluble materials in the dry product is preferably such that, on solution in water the water-insoluble materials have a particle size of less than 1 micron as determined by the Malvern method described herein.
  • the determined particle size is less than 800 nm, more preferably less than 500 nm.
  • the particle size is in the range 250-50 nm and is most preferably in the range 200-75 nm.
  • the broader range is analogous to the size of a virus particle (which typically range from 450-20 nm). Diameters of less than 200 nm are most preferred. It is believed that there is no significant reduction of particle size for the biocidal agent on dispersion of the solid form in water.
  • Very small particle sizes of as low as 4 nm can be obtained by the method of the invention.
  • the compositions of the invention show a further improvement in efficacy.
  • solution form will be a form suitable for use either ‘as is’ or following further dilution or admixture with other components.
  • the present invention therefore also relates to a method for the delivery of a water-insoluble biocide which comprises the steps of:
  • the substrate can be the subject to be treated directly with the biocide (such as a plant, where the object is the eradication of, for example, fungi, or a wooden object requiring rot prevention treatment) or can be associated with the subject (such as bedding or soil).
  • Preferred substrates are selected from a plant (or part thereof, including seeds, bulbs, fruits, roots, leaves), soil, an animal, bedding for animals, fodder or an article manufactured from a plant or an animal.
  • Preferred treatment methods include spraying, dipping and washing.
  • a method of particle sizing for the dispersed products of the present invention used in the following examples employs a dynamic light scattering instrument (Nano S, manufactured by Malvern Instruments UK). Specifically, the Malvern Instruments Nano S uses a red (633 nm) 4 mW Helium-Neon laser to illuminate a standard optical quality UV curvette containing a suspension of material.
  • the solution was spray dried using a Buchi B-290TM bench top spray-dryer, operated in a negative pressure mode. Air drawn from the lab was used as the drying medium and the operating conditions were as follows:
  • a dry white powder was obtained. This material was redispersed in demineralised water at a concentration of 10 mg/ml (1.0 wt %, 0.1 wt % chlorothalonil). This produced an opaque white dispersion. At this concentration, the material was relatively slow to disperse (approx. 5 minutes).
  • the solution was spray dried using a Buchi B-290 bench top spray dryer, operated in a negative pressure mode. Air drawn from the lab was used as the drying medium.
  • a dry white powder was obtained. This material was redispersed in demineralised water at a concentration of 1 mg/ml (0.1 wt %, 0.01 wt % chlorothalonil). This produced an opaque white dispersion. At this concentration, the material was considerably quicker (than example 1) to disperse (less than 30 seconds).
  • the solution was spray dried using a Buchi B-290 bench top spray dryer, operated in a negative pressure mode. Air drawn from the lab was used as the drying medium.
  • a dry white powder was obtained. This material was redispersed in demineralised water at a concentration of 1 mg/ml (0.1 wt %, 0.01 wt % chlorothalonil). This produced an opaque white dispersion. At this concentration, the material dispersed at a similar rate to example 2 (less than 30 seconds).
  • Ketoconazole 100 mg (10%) Ketoconazole, 500 mg (50%) poly(ethylene glycol) (10 kDa, Fluka) and 400 mg (40%) sodium lauryl ether sulfate (SLES) were dissolved in 60 ml ethanol and 60 ml water. The resulting solution was spray dried at an inlet temperature of 180° C. and a pump rate of approximately 3.6 ml/minute. The recovered dry white powder redispersed in water to give a clear suspension of average particle size 16.1 nm (Z-ave).
  • SLES sodium lauryl ether sulfate
  • MIC Minimum Inhibitory Concentration
  • CA Candida albicans
  • YEME yeast extract malt extract media
  • concentrations of the active material and blanks contained in a 96 well plate were incubated at 37° C. overnight, and then examined with a UV plate reader at a wavelength of 550 nm. Concentrations of biocide that inhibited cell growth resulted in a well with very low optical density (visually clear), whereas wells in which cells growth occurred had a very high optical density (visually opaque).
  • the MIC was defined as the lowest concentration of biocide that resulted in total inhibition of cell growth, when incubated overnight.
  • Particle size Material Initial concentration (Z-ave, nm) MIC (mg/L) 13/28/20 equivalent to 0.15 mg/ml n/a no inhibition (SLES/PEG active observed blank matrix) As Example 5 0.15 mg/ml active 16.1 ⁇ 14 As Example 4 0.15 mg/ml active 24.2 ⁇ 38 DMSO 25% v/v n/a ⁇ 9.25% v/v PVA (blank) equivalent to 0.15 mg/ml n/a no inhibition active observed Ketoconazole 0.15 mg/ml in 25% v/v n/a 65 in DMSO solvent
  • biocidal activity of the materials according to the present invention is influenced by the composition of its matrix.
  • the activity of the formulation increased 3 fold when the proportion of surfactant is increased from 10 wt. % to 80 wt. %.
  • the solution was spray dried using a Buchi B-290 bench top spray dryer, operated in a negative pressure mode. Air drawn from the lab was used as the drying medium.
  • Phase 1 10% ISP (28) 500 mg in 10 ml Chloroform Phase 2: 60% PVA (10 kDa) 3000 mg 30% SDS 1500 mg in 75 ml water
  • Emulsification was achieved by sonicating for 5 minutes at 50% power, then for a further 2 minutes at 100% power (using a 1 kW probe type sonicator).
  • the resulting emulsion was spray dried at an inlet temperature of 150° C. and a pump rate of 5.6 ml/min. Aspiration and atomisation gas were set to maximum.
  • the resulting dry white powder redispersed to give a slightly cloudy suspension at a concentration of 1 mg/ml.
  • the particle size was measured as 297+/ ⁇ 8.66 nm
  • Formulation was as Example 13, but contained a small quantity of additional volatile cosurfactant (n-butanol).
  • Phase 1 10% ISP (28) 500 mg in 10 ml Chloroform and 2 ml n-butanol Phase 2: 60% PVA (10 kDa) 3000 mg 30% SDS 1500 mg in 75 ml water
  • the two phases were continuously cooled using a water jacketed beaker whilst being emulsified. Emulsification was achieved by sonicating for 5 minutes at 50% power, then for a further 2 minutes at 100% power (using a 1 kW probe type sonicator).
  • the resulting emulsion was spray dried at an inlet temperature of 150° C. and a pump rate of 5.6 ml/min. Aspiration and atomisation gas were set to maximum.
  • the resulting dry white powder redispersed to give a slightly cloudy suspension at a concentration of 1 mg/ml, although noticeably clearer than that of example 13.
  • the particle size was measured as 252+/ ⁇ 14.0 nm.
  • a single phase solution of the insecticide ⁇ -cyhalothrin, PEG and the PEG based surfactants PluronicTM F68 and PluronicTM F127 was prepared in chloroform. This was freeze dried using a “Christ alpha 2-4 LSC” freeze dryer in single batches on a 5 ml per sample scale (i.e. 250 mg solids in each sample).
  • Example Particle 17 F68 F127 PEG active size A 0.9 0 0 0.1 66.19 B 0 0.9 0 0.1 44.24 C 0 0 0.9 0.1 168.2 D 0.7 0 0 0.3 102 E 0 0.7 0 0.3 80.99 F 0 0 0.7 0.3 240.5 G 0 0.4 0.4 0.2 94.59 H 0.4 0 0.4 0.2 127.5 I 0.3 0.3 0.3 0.1 51.87 J 0.26667 0.26667 0.2667 0.2 90.92 K 0.26667 0.26667 0.2667 0.2 93.54 L 0.26667 0.26667 0.2667 0.2 72.5

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080262100A1 (en) * 2005-01-28 2008-10-23 Andrew Ian Cooper Method of Preparing Carrier Liquids
US8084397B2 (en) 2008-09-25 2011-12-27 Vive Nano, Inc. Methods to produce polymer nanoparticles and formulations of active ingredients
US20130196852A1 (en) * 2010-10-05 2013-08-01 Iota Nanosolutions Limited Processes for preparing improved compositions
US10315330B2 (en) * 2014-12-23 2019-06-11 Dow Global Technologies Llc Treated porous material
US10455830B2 (en) 2011-08-23 2019-10-29 Vive Crop Protection Inc. Pyrethroid formulations
US11344028B2 (en) 2011-12-22 2022-05-31 Vive Crop Protection Inc. Strobilurin formulations
US11517013B2 (en) 2017-08-25 2022-12-06 Vive Crop Protection Inc. Multi-component, soil-applied, pesticidal compositions

Families Citing this family (88)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090130212A1 (en) * 2006-05-15 2009-05-21 Physical Pharmaceutica, Llc Composition and improved method for preparation of small particles
GB0613925D0 (en) * 2006-07-13 2006-08-23 Unilever Plc Improvements relating to nanodispersions
WO2008022651A1 (en) 2006-08-21 2008-02-28 Antoine Turzi Process and device for the preparation of platelet rich plasma for extemporaneous use and combination thereof with skin and bone cells
AR063704A1 (es) 2006-09-14 2009-02-11 Makhteshim Chem Works Ltd Nanoparticulas de pesticida obtenida obtenidas a partir de microemulsiones y nanoemulsiones
CA2665841C (en) 2006-10-09 2016-04-05 Charleston Laboratories, Inc. Pharmaceutical compositions
WO2009081283A2 (en) * 2007-06-18 2009-07-02 Combino Pharm, S.L. Aqueous formulations of acetaminophen for injection
EP2170313A2 (en) * 2007-06-18 2010-04-07 Combino Pharm, S.L. Aqueous formulations of acetaminophen for injection
AU2008303129B2 (en) 2007-09-25 2013-08-01 Formulex Pharma Innovations Ltd. Compositions comprising lipophilic active compounds and method for their preparation
JP5714910B2 (ja) 2008-01-09 2015-05-07 チャールストン ラボラトリーズ，インコーポレイテッド 薬学的組成物
TR200800634A2 (tr) * 2008-01-30 2009-02-23 Takka Sevgi̇ Uzatılmış salım sağlayan fluvastatin tablet.
US8372432B2 (en) 2008-03-11 2013-02-12 Depomed, Inc. Gastric retentive extended-release dosage forms comprising combinations of a non-opioid analgesic and an opioid analgesic
EP2262484B1 (en) * 2008-03-11 2013-01-23 Depomed, Inc. Gastric retentive extended-release dosage forms comprising combinations of a non-opioid analgesic and an opioid analgesic
AU2009269473B2 (en) * 2008-07-11 2012-02-16 Nippon Soda Co., Ltd. Method of manufacture of sustained-release formulation composition
GB0814953D0 (en) * 2008-08-18 2008-09-24 Unilever Plc Improvements relating to nanodisperse compositions
FR2938433B1 (fr) * 2008-11-19 2011-09-09 Francois Fauran Compositions pharmaceutiques utilisant l'inuline comme excipient de granulation
AU2009337187B2 (en) * 2008-12-12 2014-10-23 Azelis New Zealand Limited Compositions for the treatment of timber and other wood substrates
EP2243477A1 (de) 2009-04-22 2010-10-27 Fresenius Kabi Deutschland GmbH Paracetamol zur parenteralen Verabreichung
CN102458373A (zh) * 2009-05-27 2012-05-16 株式会社三养生物制药 生物利用度提高的包含难溶性药物的微球及其制备方法
HUP0900384A2 (en) * 2009-06-19 2011-01-28 Nangenex Nanotechnologiai Zartkoerueen Muekoedoe Reszvenytarsasag Nanoparticulate olmesartan medoxomil compositions
HUP0900376A2 (en) * 2009-06-19 2011-01-28 Nangenex Nanotechnologiai Zartkoerueen Muekoedoe Reszvenytarsasag Nanoparticulate candesartan cilexetil composition
US20120095067A1 (en) * 2009-06-25 2012-04-19 Jin Yang Pharm. Co., Ltd. Pharmaceutical composition containing carboxylosartan and a production method therefor
WO2011006012A1 (en) 2009-07-08 2011-01-13 Charleston Laboratories Inc. Pharmaceutical compositions
US20110052685A1 (en) * 2009-08-31 2011-03-03 Depomed, Inc. Gastric retentive pharmaceutical compositions for immediate and extended release of acetaminophen
JP5498769B2 (ja) * 2009-12-04 2014-05-21 花王株式会社 脂溶性薬物内包ナノ粒子の製造方法
US8597681B2 (en) 2009-12-22 2013-12-03 Mallinckrodt Llc Methods of producing stabilized solid dosage pharmaceutical compositions containing morphinans
US9198861B2 (en) 2009-12-22 2015-12-01 Mallinckrodt Llc Methods of producing stabilized solid dosage pharmaceutical compositions containing morphinans
EP2536396B1 (en) 2010-02-16 2016-08-10 KRKA, D.D., Novo Mesto Process for the preparation of oral solid dosage forms comprising valsartan
JP5602936B2 (ja) 2010-03-29 2014-10-08 フイルメニツヒ ソシエテ アノニム 噴霧乾燥した結晶性活性成分
GB201006038D0 (en) 2010-04-12 2010-05-26 Unilever Plc Improvements relating to antiviral compositions
UA111167C2 (uk) * 2010-08-05 2016-04-11 ДАУ АГРОСАЙЄНСІЗ ЕлЕлСі Пестицидні композиції мезорозмірних частинок з підсиленою дією
US8877221B2 (en) 2010-10-27 2014-11-04 Warsaw Orthopedic, Inc. Osteoconductive matrices comprising calcium phosphate particles and statins and methods of using the same
US9107983B2 (en) 2010-10-27 2015-08-18 Warsaw Orthopedic, Inc. Osteoconductive matrices comprising statins
WO2012082765A2 (en) 2010-12-16 2012-06-21 The United State Of America. As Represented By The Secretary Department Of Health And Human Services Methods for decreasing body weight and treating diabetes
JP6129155B2 (ja) 2011-04-12 2017-05-17 ライジェル ファーマシューティカルズ， インコーポレイテッド 同種移植片拒絶反応を抑制する方法
US8741885B1 (en) 2011-05-17 2014-06-03 Mallinckrodt Llc Gastric retentive extended release pharmaceutical compositions
US8858963B1 (en) 2011-05-17 2014-10-14 Mallinckrodt Llc Tamper resistant composition comprising hydrocodone and acetaminophen for rapid onset and extended duration of analgesia
US8658631B1 (en) 2011-05-17 2014-02-25 Mallinckrodt Llc Combination composition comprising oxycodone and acetaminophen for rapid onset and extended duration of analgesia
WO2012170417A2 (en) 2011-06-06 2012-12-13 Warsaw Orthopedic, Inc. Methods and compositions to enhance bone growth comprising a statin
JP2013001771A (ja) * 2011-06-14 2013-01-07 Neos Co Ltd 液状カビ防除洗浄剤組成物
RU2469536C1 (ru) * 2011-06-16 2012-12-20 Государственное бюджетное учреждение Республики Башкортостан "Научно-исследовательский технологический институт гербицидов и регуляторов роста растений с опытно-экспериментальным производством Академии наук Республики Башкортостан" Фунгицидное средство и способ его получения
EA032840B8 (ru) 2011-06-22 2020-06-18 Вайоми Терапеутикс Лимитед Пролекарства на основе конъюгатов противогрибковых агентов и их применение
GB201115079D0 (en) 2011-08-31 2011-10-19 Iota Nanosolutions Ltd Method of preparing carrier liquids
GB201115633D0 (en) 2011-09-09 2011-10-26 Univ Liverpool Compositions of efavirenz
GB201115634D0 (en) 2011-09-09 2011-10-26 Univ Liverpool Compositions of lopinavir
GB201115635D0 (en) 2011-09-09 2011-10-26 Univ Liverpool Compositions of lopinavir and ritonavir
US8609684B2 (en) 2011-12-12 2013-12-17 PruGen IP Holdings, Inc. Solubilization and bioavailability of acetaminophen
MX2014013826A (es) * 2012-05-16 2018-04-24 Singh Mewa Composiciones farmaceuticas para la entrega de farmacos sustancialmente solubles en agua.
PL2872121T3 (pl) 2012-07-12 2019-02-28 SpecGx LLC Kompozycje farmaceutyczne o przedłużonym uwalnianiu, zniechęcające do nadużywania
US20140073678A1 (en) * 2012-09-12 2014-03-13 Monosol Rx, Llc Anti-pain and anti-nausea and/or vomiting combinatorial compositions
US20160128944A1 (en) 2013-06-04 2016-05-12 Vyome Biosciences Pvt. Ltd. Coated particles and compositions comprising same
US10195153B2 (en) 2013-08-12 2019-02-05 Pharmaceutical Manufacturing Research Services, Inc. Extruded immediate release abuse deterrent pill
MX2016005101A (es) 2013-10-21 2017-01-09 Salk Inst For Biological Studi Factor de crecimiento de fibroblastos (fgf) 1 mutado y procedimientos de uso.
EP4173619A3 (en) * 2013-11-13 2023-07-19 National Defense Education and Research Foundation New acetaminophen compound composition without side effect to liver
US9492444B2 (en) 2013-12-17 2016-11-15 Pharmaceutical Manufacturing Research Services, Inc. Extruded extended release abuse deterrent pill
WO2015095391A1 (en) 2013-12-17 2015-06-25 Pharmaceutical Manufacturing Research Services, Inc. Extruded extended release abuse deterrent pill
EP3119415A4 (en) 2014-03-07 2017-11-29 The Arizona Board of Regents on behalf of the University of Arizona Non-narcotic crmp2 peptides targeting sodium channels for chronic pain
EP2952208A1 (en) * 2014-06-04 2015-12-09 Universidade de Santiago de Compostela Hydroalcoholic system for nail treatment
PT3154528T (pt) 2014-06-11 2023-06-22 SpecGx LLC Composições secas por pulverização possuindo diferentes perfis de dissolução e processos para a sua preparação
CN104042626A (zh) * 2014-07-01 2014-09-17 李绍明 杀菌抑菌剂
CA2955229C (en) 2014-07-17 2020-03-10 Pharmaceutical Manufacturing Research Services, Inc. Immediate release abuse deterrent liquid fill dosage form
EP3209282A4 (en) 2014-10-20 2018-05-23 Pharmaceutical Manufacturing Research Services, Inc. Extended release abuse deterrent liquid fill dosage form
JP6730315B2 (ja) * 2015-01-20 2020-07-29 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ 担体ポリマーとしてのポリビニルアルコールを用いた化合物の固体分散体
CN104798772B (zh) * 2015-03-13 2017-05-24 中国农业科学院农业环境与可持续发展研究所 一种农药纳米固体分散体及其制备方法
CA2991108A1 (en) 2015-07-02 2017-01-05 Civitas Therapeutics, Inc. Triptan powders for pulmonary delivery
US10206904B2 (en) 2015-07-17 2019-02-19 The Board Of Regents Of The University Of Oklahoma Licofelone derivatives and methods of use
CN105145553A (zh) * 2015-10-12 2015-12-16 广西田园生化股份有限公司 一种难溶农药的固体分散体组合物
PL3410851T3 (pl) * 2016-02-02 2020-12-28 Evonik Operations Gmbh Proszkowe formulacje substancji powierzchniowo czynnych na nośnikach stałych, rozpuszczalnych w wodzie, sposób ich wytwarzania i zastosowania
EP3423041A4 (en) 2016-03-04 2019-09-11 Charleston Laboratories, Inc. PHARMACEUTICAL COMPOSITIONS
JP2019518057A (ja) * 2016-06-16 2019-06-27 ザ ユニバーシティー オブ リヴァプール 化学組成物
RU2619249C1 (ru) * 2016-11-07 2017-05-12 Федеральное государственное бюджетное учреждение науки Институт химии твердого тела и механохимии Сибирского отделения Российской академии наук (ИХТТМ СО РАН) Композиция для протравливания семян и способ её получения
WO2018160772A1 (en) 2017-02-28 2018-09-07 The United State Of America, As Represented By The Secretary, Department Of Health & Human Services Method of treating obesity, insulin resistance, non-alcoholic fatty liver disease including non-alcoholic steatohepatitis
WO2018178722A1 (en) 2017-03-31 2018-10-04 The University Of Liverpool Prodrug compositions
WO2018232053A2 (en) * 2017-06-15 2018-12-20 Savior Lifetec Corporation Methods for producing particles of an active ingredient
US20210361639A1 (en) 2018-03-02 2021-11-25 The University Of Liverpool Solid compositions of actives, processes for preparing same and uses of such solid compositions
JP6858729B2 (ja) * 2018-05-25 2021-04-14 ▲財▼▲団▼法人国防教育研究基金会Ｎａｔｉｏｎａｌ Ｄｅｆｅｎｓｅ Ｅｄｕｃａｔｉｏｎ Ａｎｄ Ｒｅｓｅａｒｃｈ Ｆｏｕｎｄａｔｉｏｎ 肝臓に対する副作用がない、新しいアセトアミノフェン複合組成
CN113260257B (zh) * 2018-12-28 2022-09-06 南京善思生物科技有限公司 纳米农药制剂及其制备方法
CN109846821B (zh) * 2019-01-03 2021-07-06 昆药集团股份有限公司 一种蒿甲醚纳米制剂及其制备方法
US20220054494A1 (en) 2019-03-13 2022-02-24 University Of Pittsburgh - Of The Commonwealth System Of Higher Education Methods for treating bladder and urethra dysfunction and disease
CN110074993A (zh) * 2019-06-05 2019-08-02 山东大学 一种制备紫外吸收剂纳米颗粒的方法
MX2021015576A (es) * 2019-06-28 2022-03-02 Solstar Pharma Formulacion gastroretentiva de liberacion extendida contra helicobacter pylori.
WO2021062012A1 (en) 2019-09-25 2021-04-01 Emory University Use of klk10 and engineered derivatizations thereof
JPWO2021085395A1 (zh) * 2019-10-28 2021-05-06
EP4090381A1 (en) 2020-01-17 2022-11-23 The United States of America, as represented by the Secretary, Department of Health and Human Services <smallcaps/>? ? ?crx-? ? ? ? ?gene therapy for treatment ofautosomal dominant retinopathies
WO2021225781A2 (en) 2020-05-07 2021-11-11 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Aberrant post-translational modifications (ptms) in methyl- and propionic acidemia and a mutant sirtuin (sirt) to metabolize ptms
IT202000022789A1 (it) 2020-09-28 2020-12-28 Vitop Moulding Srl Rubinetto erogatore provvisto di sistema di collocamento, bloccaggio e orientamento su scatole di tipo Bag-In-Box
GB202115049D0 (en) 2021-10-20 2021-12-01 Univ Liverpool Chemical Compositions
WO2023196898A1 (en) 2022-04-07 2023-10-12 The United States Of America, As Represented By The Secretary, Department Of Health And Human Services Beta globin mimetic peptides and their use
CN114732009B (zh) * 2022-06-13 2022-08-23 山东百农思达生物科技有限公司 一种含有吡唑醚菌酯和烯酰吗啉的水分散粒剂的制备方法

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3720703A (en) * 1969-07-10 1973-03-13 Nat Res Dev Insecticides
US4230687A (en) * 1978-05-30 1980-10-28 Griffith Laboratories U.S.A., Inc. Encapsulation of active agents as microdispersions in homogeneous natural polymeric matrices
US4830858A (en) * 1985-02-11 1989-05-16 E. R. Squibb & Sons, Inc. Spray-drying method for preparing liposomes and products produced thereby
US5317004A (en) * 1989-01-24 1994-05-31 Griffin Corporation Microencapsulated yellow polymorphic form of trifluralin
US5532205A (en) * 1993-03-03 1996-07-02 Zeneca Limited Herbicidal composition containing glyphosate or a salt thereof
WO1997001277A1 (en) * 1995-06-29 1997-01-16 Novartis Ag Crop protection products
US20020041896A1 (en) * 1999-05-27 2002-04-11 Acusphere, Inc. Porous paclitaxel matrices and methods of manufacture thereof
US6395300B1 (en) * 1999-05-27 2002-05-28 Acusphere, Inc. Porous drug matrices and methods of manufacture thereof
US20020142050A1 (en) * 1999-05-27 2002-10-03 Acusphere Inc. Porous drug matrices and methods of manufacture thereof
US20040242427A1 (en) * 2001-11-07 2004-12-02 Sebastian Koltzenburg Cinidon-ethyl containing solid crop protection formulations and corresponding dispersions
US20040266626A1 (en) * 2001-11-07 2004-12-30 Wolfgang Schrof Solid crop protection formulations and dispersion formulations and their use in agriculture
WO2005046328A1 (de) * 2003-10-30 2005-05-26 Basf Aktiengesellschaft Nanopartikuläre wirkstoffformulierungen

Family Cites Families (80)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB501835A (en) 1936-05-29 1939-03-02 Siemens Ag Process and apparatus for reducing the power required for the mechanical treatment of movable masses
GB1554662A (en) * 1976-05-05 1979-10-24 Inverni Della Beffa Spa Polyhydroxyphenylchromanones
DE3439482A1 (de) 1984-10-27 1986-05-07 Röhm GmbH, 6100 Darmstadt Verfahren zur beschichtung von substraten mit kratzfesten, nichtreflektierenden ueberzuegen
GB8918807D0 (en) * 1989-08-17 1989-09-27 Shell Int Research A solid pesticidal formulation,a process for its preparation and the use thereof
JP3067810B2 (ja) * 1990-12-21 2000-07-24 中外製薬株式会社 経口投与用ｏ／ｗ型エマルジョンの乾燥粉末製造法
DE4329446A1 (de) * 1993-09-01 1995-03-02 Basf Ag Verfahren zur Herstellung von feinteiligen Farb- oder Wirkstoffzubereitungen
US5858398A (en) * 1994-11-03 1999-01-12 Isomed Inc. Microparticular pharmaceutical compositions
WO1997013503A1 (en) 1995-10-13 1997-04-17 The Penn State Research Foundation Synthesis of drug nanoparticles by spray drying
GB9606188D0 (en) 1996-03-23 1996-05-29 Danbiosyst Uk Pollysaccharide microspheres for the pulmonary delivery of drugs
US5858409A (en) * 1996-04-17 1999-01-12 Fmc Corporation Hydrolyzed cellulose granulations for pharmaceuticals
WO1998029141A1 (en) 1996-12-31 1998-07-09 Inhale Therapeutic Systems, Inc. Processes for spray drying solutions of hydrophobic drugs with hydrophilic excipients and compositions prepared by such processes
JP4183279B2 (ja) * 1997-04-15 2008-11-19 アール ピー シェーラー テクノロジーズ インコーポレーテッド 医薬用加水分解セルロース顆粒
EP1080720A4 (en) * 1998-03-05 2002-06-05 Nippon Shinyaku Co Ltd FAT EMULSIONS FOR INHALATIVE ADMINISTRATION
JPH11322587A (ja) 1998-05-18 1999-11-24 Sumitomo Chem Co Ltd 常温で固体の生理活性物質のマイクロカプセル化方法およびこの方法により得られるマイクロカプセル組成物
WO2000040220A1 (en) * 1999-01-06 2000-07-13 Korea Research Institute Of Chemical Technology Method of preparing pharmaceutical active ingredient comprising water-insoluble drug and pharmaceutical composition for oral administration comprising the same
ATE400252T1 (de) * 1999-02-10 2008-07-15 Pfizer Prod Inc Pharmazeutische feste dispersionen
GB9904012D0 (en) 1999-02-22 1999-04-14 Zeneca Ltd Agrochemical formulation
EP1180020B2 (en) 1999-05-27 2009-06-24 Acusphere, Inc. Porous drug matrices and methods of manufacture thereof
GB9915231D0 (en) * 1999-06-29 1999-09-01 Pfizer Ltd Pharmaceutical complex
GB9920148D0 (en) * 1999-08-25 1999-10-27 Smithkline Beecham Plc Novel composition
WO2001039836A1 (en) 1999-12-01 2001-06-07 Natco Pharma Limited A rapid acting freeze dired oral pharmaceutical composition for treating migraine
KR100694667B1 (ko) * 1999-12-08 2007-03-14 동아제약주식회사 생체내이용률 향상과 개인간 및 개인내 흡수 편차를감소시킨 이트라코나졸 함유 항진균성 제제
US6207674B1 (en) 1999-12-22 2001-03-27 Richard A. Smith Dextromethorphan and oxidase inhibitor for weaning patients from narcotics and anti-depressants
WO2001089484A2 (en) * 2000-05-22 2001-11-29 Verion, Inc. Method for increasing the compressibility of poorly binding powder materials
US6932963B2 (en) * 2000-06-23 2005-08-23 Nicholas V. Perricone Treatment of skin wounds using polyenylphosphatidylcholine and alkanolamines
IT1318618B1 (it) * 2000-07-10 2003-08-27 A C R Applied Coating Res S A Microsfere bioadesive a rilascio rapido per la somministrazionesublinguale di principi attivi.
JP5070670B2 (ja) * 2000-07-24 2012-11-14 小野薬品工業株式会社 Ｎ−［ｏ−（ｐ−ピバロイルオキシベンゼンスルホニルアミノ）ベンゾイル］グリシン・モノナトリウム塩・４水和物の凍結乾燥製剤およびその製造方法
DE10036871A1 (de) * 2000-07-28 2002-02-14 Pharmasol Gmbh Dispersionen zur Formulierung wenig oder schwer löslicher Wirkstoffe
DE60129573T2 (de) * 2000-09-20 2008-04-17 Jagotec Ag Verfahren zur sprühtrocknung von zusammensetzungen enthaltend fenofibrat
US6756062B2 (en) * 2000-11-03 2004-06-29 Board Of Regents University Of Texas System Preparation of drug particles using evaporation precipitation into aqueous solutions
US8067032B2 (en) * 2000-12-22 2011-11-29 Baxter International Inc. Method for preparing submicron particles of antineoplastic agents
AU2002243760A1 (en) * 2001-01-30 2002-08-12 Board Of Regents University Of Texas System Process for production of nanoparticles and microparticles by spray freezing into liquid
US6355675B1 (en) 2001-05-15 2002-03-12 Isp Investments Inc. Emulsifiable concentrate of a water-insoluble fungicide
EP1411900B2 (en) 2001-06-01 2013-12-04 Pozen, Inc. PHARMACEUTICAL COMPOSITIONS FOR THE COORDINATED DELIVERY OF NSAIDs
HUP0400264A2 (hu) * 2001-06-22 2004-08-30 Pfizer Products Inc. Alacsony oldékonyságú és/vagy savra érzékeny hatóanyagokat és semlegesített savas polimereket tartalmazó gyógyszerkészítmények és eljárás az előállításukra
KR100425226B1 (ko) * 2001-07-03 2004-03-30 주식회사 팜트리 아세클로페낙을 함유하는 경제적인 경구용 제제의 조성 및제법
WO2003017659A1 (en) * 2001-08-21 2003-02-27 Sony Corporation Information processing system, information processing apparatus, and method
JP2005504090A (ja) * 2001-09-26 2005-02-10 バクスター・インターナショナル・インコーポレイテッド 分散体および溶媒相または液相の除去によるサブミクロンサイズ−ナノ粒子の調製
US20060003012A9 (en) * 2001-09-26 2006-01-05 Sean Brynjelsen Preparation of submicron solid particle suspensions by sonication of multiphase systems
DE10151392A1 (de) * 2001-10-18 2003-05-08 Bayer Cropscience Ag Pulverförmige Feststoff-Formulierungen
ATE403432T1 (de) * 2002-02-01 2008-08-15 Pfizer Prod Inc Pharmazeutische darreichungsform mit gesteuerter freigabe eines cholesterylester- transferproteininhibitors
BR0307333A (pt) * 2002-02-01 2004-12-07 Pfizer Prod Inc Métodos para a preparação de dispersões homogéneas de fármacos sólidos amorfos atomizados utilizando um sistema de secagem por pulverização
US6780324B2 (en) * 2002-03-18 2004-08-24 Labopharm, Inc. Preparation of sterile stabilized nanodispersions
US20040028505A1 (en) * 2002-06-07 2004-02-12 Bilbrey Robert A. Document tape binding system with automatic tape feed, tape indicia sensing, spine printing method and post-bind automation mechanisms
JP4831965B2 (ja) 2002-06-10 2011-12-07 エラン ファーマ インターナショナル，リミティド ＨＭＧ−ＣｏＡ還元酵素インヒビター誘導体（「スタチン」）を含むナノ粒子製剤、その新規組合せ、ならびにこれらの医薬組成物の製造
US20030017208A1 (en) * 2002-07-19 2003-01-23 Francis Ignatious Electrospun pharmaceutical compositions
DE10244681A1 (de) * 2002-09-24 2004-04-08 Boehringer Ingelheim International Gmbh Neue feste Telmisartan enthaltende pharmazeutische Formulierungen und deren Herstellung
AU2003268380A1 (en) * 2002-10-04 2004-05-04 Elan Pharma International Limited Gamma irradiation of solid nanoparticulate active agents
CN1176649C (zh) 2002-10-16 2004-11-24 上海医药工业研究院 舒马普坦干粉吸入剂及其制备方法
JP2006514698A (ja) * 2002-10-30 2006-05-11 スフェリックス， インコーポレイテッド ナノ粒子生物活性物質
MXPA05006954A (es) 2002-12-26 2005-09-22 Pozen Inc Formas de dosificacion de capas multiples que contienen nsaids y triptanos.
EP2263687B1 (en) * 2002-12-27 2015-03-25 Novartis Vaccines and Diagnostics, Inc. Immunogenic compositions containing phospholipid
US20060210620A1 (en) * 2003-01-21 2006-09-21 Kumra Pannanchukunnath M Co-precipitated amorphous losartan and dosage forms comprising the same
US20040197301A1 (en) * 2003-02-18 2004-10-07 Zhong Zhao Hybrid polymers and methods of making the same
JP2006523620A (ja) * 2003-02-19 2006-10-19 バイオヴェイル ラボラトリーズ インコーポレイテッド 急速吸収選択的５−ｈｔ作用剤製剤
WO2004075921A1 (en) * 2003-02-26 2004-09-10 Vrije Universiteit Brussel Inclusion complex of artemisinin or derivates thereof with cyclodextrins
MXPA05010821A (es) * 2003-04-08 2006-03-30 Progenics Pharm Inc Terapia de combinacion para constipacion que comprende un laxante y un antagonista opioide periferico.
US20040247624A1 (en) * 2003-06-05 2004-12-09 Unger Evan Charles Methods of making pharmaceutical formulations for the delivery of drugs having low aqueous solubility
CA2465565A1 (en) 2003-06-12 2004-12-12 Warner-Lambert Company Llc Pharmaceutical compositions of atorvastatin
EP1648515B1 (en) * 2003-07-16 2012-11-21 Boehringer Ingelheim International GmbH Chlorthalidone combinations
US7687167B2 (en) * 2003-07-18 2010-03-30 Panasonic Corporation Power supply unit
CL2004001884A1 (es) 2003-08-04 2005-06-03 Pfizer Prod Inc Procedimiento de secado por pulverizacion para la formacion de dispersiones solidas amorfas de un farmaco y polimeros.
DE10338403A1 (de) * 2003-08-18 2005-03-17 Boehringer Ingelheim Pharma Gmbh & Co. Kg Pulverformulierung, enthaltend den CGRP-Antagonisten 1-[N2-[3,5-Dibrom-N-[[4-(3,4-dihydro-2(1H)-oxochinazolin-3-yl]-1-piperidinyl]carbonyl]-D-tyrosyl]-L-lysyl]-4-(4-pyrindinyl)-piperazin, Verfahren zu dessen Herstellung sowie dessen Verwendung als Inhalativum
DE10351087A1 (de) * 2003-10-31 2005-05-25 Bayer Technology Services Gmbh Feste Wirkstoff-Formulierung
KR100603974B1 (ko) * 2003-12-05 2006-07-25 김갑식 고체상 지질을 용매로 이용한 나노수준의 또는 비결정질입자의 제조 방법
MXPA06007512A (es) * 2003-12-31 2006-08-31 Pfizer Prod Inc Composiciones solidas farmaceuticas estabilizadas de farmacos de baja solubilidad, poloxameros y polimeros estabilizadores.
KR100629771B1 (ko) * 2004-01-27 2006-09-28 씨제이 주식회사 결정성이 감소되거나 무정형화된 올티프라즈의 제조방법
IL160095A0 (en) 2004-01-28 2004-06-20 Yissum Res Dev Co Formulations for poorly soluble drugs
JP2005298347A (ja) * 2004-04-06 2005-10-27 Yoshiaki Kawashima 吸入製剤及びその製造方法
KR100598326B1 (ko) 2004-04-10 2006-07-10 한미약품 주식회사 ＨＭＧ-ＣｏＡ 환원효소 억제제의 경구투여용 서방형 제제및 이의 제조방법
AU2005237213B2 (en) 2004-04-28 2008-04-24 Unilever Plc Edible oil containing statins
WO2005117834A1 (en) * 2004-05-27 2005-12-15 Janssen Pharmaceutica N.V. Solid dispersions of a basic drug compound and a polymer containing acidic groups
CA2560984A1 (en) 2004-06-01 2005-12-15 Teva Gyogyszergyar Zartkoruen Mukodo Reszvenytarsasag Process for preparation of amorphous form of a drug
DE102004031298A1 (de) 2004-06-28 2006-01-12 Basf Ag Wässrige Dispersionen schwer wasserlöslicher oder wasserunlöslicher Wirkstoffe und daraus hergestellte Trockenpulver enthaltend mindestens ein Polyethergruppen enthaltendes Polymer als Schutzkolloid
AU2005290583A1 (en) * 2004-10-01 2006-04-13 Eisai R & D Management Co., Ltd. Fine particles-containing composition and manufacturing method therefor
US20060105038A1 (en) * 2004-11-12 2006-05-18 Eurand Pharmaceuticals Limited Taste-masked pharmaceutical compositions prepared by coacervation
EA200701442A1 (ru) * 2005-01-06 2008-02-28 Элан Фарма Интернэшнл Лтд. Композиции наночастиц кандесартана
GB0501835D0 (en) * 2005-01-28 2005-03-09 Unilever Plc Improvements relating to spray dried compositions
GB0613925D0 (en) * 2006-07-13 2006-08-23 Unilever Plc Improvements relating to nanodispersions
US20080152717A1 (en) * 2006-12-14 2008-06-26 Isp Investments, Inc. Amorphous valsartan and the production thereof

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3720703A (en) * 1969-07-10 1973-03-13 Nat Res Dev Insecticides
US4230687A (en) * 1978-05-30 1980-10-28 Griffith Laboratories U.S.A., Inc. Encapsulation of active agents as microdispersions in homogeneous natural polymeric matrices
US4830858A (en) * 1985-02-11 1989-05-16 E. R. Squibb & Sons, Inc. Spray-drying method for preparing liposomes and products produced thereby
US5317004A (en) * 1989-01-24 1994-05-31 Griffin Corporation Microencapsulated yellow polymorphic form of trifluralin
US5532205A (en) * 1993-03-03 1996-07-02 Zeneca Limited Herbicidal composition containing glyphosate or a salt thereof
WO1997001277A1 (en) * 1995-06-29 1997-01-16 Novartis Ag Crop protection products
US20020142050A1 (en) * 1999-05-27 2002-10-03 Acusphere Inc. Porous drug matrices and methods of manufacture thereof
US6395300B1 (en) * 1999-05-27 2002-05-28 Acusphere, Inc. Porous drug matrices and methods of manufacture thereof
US20020041896A1 (en) * 1999-05-27 2002-04-11 Acusphere, Inc. Porous paclitaxel matrices and methods of manufacture thereof
US6645528B1 (en) * 1999-05-27 2003-11-11 Acusphere, Inc. Porous drug matrices and methods of manufacture thereof
US20050048116A1 (en) * 1999-05-27 2005-03-03 Julie Straub Porous drug matrices and methods of manufacture thereof
US20050058710A1 (en) * 1999-05-27 2005-03-17 Acusphere, Inc. Porous drug matrices and methods of manufacture thereof
US6932983B1 (en) * 1999-05-27 2005-08-23 Acusphere, Inc. Porous drug matrices and methods of manufacture thereof
US20040242427A1 (en) * 2001-11-07 2004-12-02 Sebastian Koltzenburg Cinidon-ethyl containing solid crop protection formulations and corresponding dispersions
US20040266626A1 (en) * 2001-11-07 2004-12-30 Wolfgang Schrof Solid crop protection formulations and dispersion formulations and their use in agriculture
WO2005046328A1 (de) * 2003-10-30 2005-05-26 Basf Aktiengesellschaft Nanopartikuläre wirkstoffformulierungen
US20070122436A1 (en) * 2003-10-30 2007-05-31 Sebastian Koltzenburg Nanoparticulate active substance formulations

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080262100A1 (en) * 2005-01-28 2008-10-23 Andrew Ian Cooper Method of Preparing Carrier Liquids
US10070650B2 (en) 2008-09-25 2018-09-11 Vive Crop Protection Inc. Methods to produce polymer nanoparticles and formulations of active ingredients
US8741808B2 (en) 2008-09-25 2014-06-03 Vive Crop Protection Inc. Methods to produce polymer nanoparticles and formulations of active ingredients
US9363994B2 (en) 2008-09-25 2016-06-14 Vive Crop Protection Inc. Nanoparticle formulations of active ingredients
US9648871B2 (en) 2008-09-25 2017-05-16 Vive Crop Protection Inc. Methods to produce polymer nanoparticles and formulations of active ingredients
US8084397B2 (en) 2008-09-25 2011-12-27 Vive Nano, Inc. Methods to produce polymer nanoparticles and formulations of active ingredients
US20130196852A1 (en) * 2010-10-05 2013-08-01 Iota Nanosolutions Limited Processes for preparing improved compositions
US10455830B2 (en) 2011-08-23 2019-10-29 Vive Crop Protection Inc. Pyrethroid formulations
US10966422B2 (en) 2011-08-23 2021-04-06 Vive Crop Protection Inc. Pyrethroid formulations
US11503825B2 (en) 2011-08-23 2022-11-22 Vive Crop Protection Inc. Pyrethroid formulations
US11344028B2 (en) 2011-12-22 2022-05-31 Vive Crop Protection Inc. Strobilurin formulations
US10315330B2 (en) * 2014-12-23 2019-06-11 Dow Global Technologies Llc Treated porous material
US11517013B2 (en) 2017-08-25 2022-12-06 Vive Crop Protection Inc. Multi-component, soil-applied, pesticidal compositions

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