WO2008135093A1 - Produits comprenant une composition anti-microbienne à base de nanoparticules de dioxyde de titane - Google Patents

Produits comprenant une composition anti-microbienne à base de nanoparticules de dioxyde de titane Download PDF

Info

Publication number
WO2008135093A1
WO2008135093A1 PCT/EP2007/054452 EP2007054452W WO2008135093A1 WO 2008135093 A1 WO2008135093 A1 WO 2008135093A1 EP 2007054452 W EP2007054452 W EP 2007054452W WO 2008135093 A1 WO2008135093 A1 WO 2008135093A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
product
product according
fatty acid
molecule
Prior art date
Application number
PCT/EP2007/054452
Other languages
English (en)
Inventor
Carlo Alberto Bignozzi
Valeria Dissette
Renato Ambrogio Della Valle
Original Assignee
Nm Tech Nanomaterials Microdevice Technology Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nm Tech Nanomaterials Microdevice Technology Ltd. filed Critical Nm Tech Nanomaterials Microdevice Technology Ltd.
Priority to PCT/EP2007/054452 priority Critical patent/WO2008135093A1/fr
Publication of WO2008135093A1 publication Critical patent/WO2008135093A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/08—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing boron
    • 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof

Definitions

  • the invention relates to nanomaterials, nanomaterial products comprising nanomaterial composition. Moreover, the invention relates to nanomaterials, nanomaterial products comprising a nanomaterial composition having antibacterial, antimicrobial, antiviral, antimycotic, germicide, photo-remediating properties.
  • the invention relates to nanomaterials, nanomaterial products, material and items comprising nanomaterial composition, such as for example plastics, fabrics, tissues and paints.
  • the invention relates to a product for topical use having antibacterial, antimicrobial, antiviral, antimycotic, germicide properties.
  • the invention relates to a material provided with a substrate having antibacterial, antimicrobial, antiviral, antimycotic, germicide properties.
  • the invention relates to a plant treating product containing Titanium Dioxide, and a method for obtaining a plant treating product.
  • the invention further relates to methods for eliminating polluting substances and for eliminating microorganisms near a surface, for example a plant and/or a leaf surface.
  • Titanium Dioxide has optimal photocatalytic properties with regard to a multiplicity of organic and inorganic pollutants, moreover Titanium Dioxide has optimal antibacterial, antimicrobial, antiviral, antimycotic, germicide properties. Owing to these properties, Titanium Dioxide-based products have already been widely used.
  • Titanium Dioxide with the properties of some metals having bacterial activity.
  • the metal ions which have the greatest antibacterial activity are, in decreasing order of potency, ions of the following metals: Hg > Ag > Cu > Zn > Fe > Pb > Bi .
  • Hg > Ag > Cu > Zn > Fe > Pb > Bi ions of the following metals.
  • the incorporation of such metals, particularly silver and copper ions, in different materials, enables elimination or reduction of the growth of bacterial colonies. This effect is particularly advantageous in light of the compatibility of Ag + and Cu 2+ with the human organism and the increasing resistance of many bacteria to antibiotics. Concerning the mechanism of action of silver, it is known that the antibacterial activity is performed by the univalent positive ion, Ag + .
  • compositions based on silver e.g. silver sulfadiazine, used to prevent infections in cases of severe burns, function with slow release of Ag + ions, which can be reversibly absorbed in bacterial cells, by association with the -SH groups of cysteine in bacterial proteins present in the cell wall.
  • the cytotoxic action of Ag + is also associated with the capability of this ion to displace essential ions from the cells, such as calcium (Ca 2+ ) and zinc (Zn 2+ ) .
  • cupric ions Cu +
  • metal oxides MO x
  • titanium dioxide zinc oxide
  • stannic oxide SnC>2
  • zirconium dioxide zirconium dioxide
  • colloidal silica colloidal silica
  • the adhesion of the Ag + ions to the nanocrystalline structure of the metal oxide is very likely associated with insertion of the ions among the nanocrystals .
  • some support does not effectively interact with known products. Therefore, non homogeneous films are applied on such supports and the properties of the product are not conferred homogeneously to the entire surface of a treated support.
  • microorganisms growth centre may develop.
  • known products are often polluting both for the environment and for the product, such as the plant, for which they are used.
  • such products may pollute the drainage waters and/or the soil also compromising the subsequent productiveness thereof, and also may be adsorbed from the plant on which they have been applied and therefore pollute the plant and the possible fruits produced by the plant.
  • known products are easily removed from the surface of the plant treated therewith, for example from the surface of the leaves of the plants, by the water, or rain that wash out such products. This implies that the plants have to be frequently and repeatedly treated with known products with consequently high costs and wastes of time.
  • known products are transported in drainage water polluting the same. Furthermore, known products do not have homogeneous structure, therefore, also on the treated substrate, microorganisms proliferation centres can develop, from which infections may spread all over the plant.
  • An object of the invention is to improve nanomaterial products.
  • Another object of the invention is to provide materials, such as for example plastics, fabrics, tissues having antibacterial, antiviral, antimycotic, properties.
  • Another object of the invention is to provide a product for topical use such as a cream, having antibacterial, antiviral, antimycotic, properties.
  • a further object of the invention is to provide a paint having antibacterial, antiviral, antimycotic, photocatalytic properties . Another object of the invention is to improve products for treating plants. Another object of the invention is to provide Titanium Dioxide-based products.
  • a further object of the invention is to provide Titanium Dioxide-based products having very good adhesion properties and that can be applied to every desired substrate forming a homogeneous film thereon.
  • a still further object of the invention is to provide a product having good adhesion properties to a lipophylic substrate . Still another object is to obtain a plant treating product that is efficacious in treating many different possible affections of the plants.
  • Still another object is to obtain a plant treating product that is efficacious for treating many different kind of plants.
  • Still another object is to obtain a product that maintains the efficacy over a considerable period of time.
  • a still another object is to provide a product that can be durably and stably adhered to a desired surface of a plant on which such a product is applied.
  • a still another object is to provide a plant treating product having a homogeneous structure and allowing a desired surface of a plant on which such a product is applied to be homogeneously covered and also any microorganism proliferation centre to be avoided.
  • a further object is to obtain a plant treating product suitable to be applied on a desired plants by spraying, and/or by rolling, and/or by brushing. Another object is to provide a product capable of avoiding any infections, for example due to fungi, microbes, acarus, mites, mildews, sponge, bacteria, insects, etc. to develop on a substrate on which the product is applied, or to which the product is mixed.
  • a method for preparing a product comprising mixing a metal or metalloid oxide AO x , metal ions Me n+ , bifunctional molecule L, that could bind both metal oxide or metalloid oxide (AO x ) and the metal ion (Me n+ ) , fatty acid molecule (FA) , so as to obtain a product containing at least a compound having general formula AO x -(L-Me ⁇ ) 1 (FA) 3 .
  • AO x is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (0) bound to the metal (A) atom; Me n+ is a metal ion, having antibacterial, antiviral, antimycotic activity; L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AO x ) and the metal ion (Me n+ ) , i is a parameter indicating the number of (L-Me n+ ) groups bound to the metal oxide AO x , (FA) is a fatty acid molecule bound to the to a AO x nanoparticles, j is a further parameter indicating the number of fatty acid molecule bound to the to a AO x nanoparticle .
  • the value of the parameter i depends on various factors, such as the size of the nanoparticle of AO x , the nature of the molecule L, and the method used for preparing the product.
  • the value of the parameter i may be the number of ligands L which the nanoparticle AO x is capable of binding to, when said nanoparticle is contacted with a solution of the ligand L for a time interval comprised in the range of 10 min to 72 hr, preferably in the range 3 to 24 hr .
  • the value of the parameter i may be comprised between about 100 and 10000.
  • the value of the further parameter j depends on various factors, such as the size of the nanoparticle of AO x , the nature of the molecule L, and the specific fatty acid molecule used.
  • the amount of fatty acid bound to the nanoparticles may be comprised between about 10 ⁇ 2 and 5% (w/w) .
  • the value of the parameter j may be comprised between about 10 and 1000, preferably between about 500 and 800.
  • the fatty acid molecule (FA) is capable of binding the nanoparticle of AO x when said AO x nanoparticle is contacted with a solution of (FA) for a time in the range of 10 min to 72 hr, preferably in the range 3 to 24 hr .
  • the nanomaterial compound according to the invention has particle size in the range 10-5000 nm, preferably a nanomaterial compound having particle size comprised between about 200 nm and 5000 nm is obtained.
  • the product having general formula AO x - (L-Me n+ ) ⁇ (FA) 3 may contain a very widely variable number of molecules of fatty acid linked to a molecule of AO x .
  • the real number of molecules of the fatty acid bound to a AO x nanoparticle depends by the size of the nanoparticles and it can be calculated that, in the case of titanium dioxide nanocrystals having diameters of the order of 25-30 nm, at least 500-800 fatty acid molecules can be organized and bound to the surface of each nanoparticle.
  • the number of fatty acid molecules which can be bound to the or AO x nanoparticle depend also by the size of the fatty acid molecules used.
  • the nanomaterial compounds according to the invention have antibacterial and antiviral activity in the presence or even in the absence of light irradiation.
  • the value of x is usually 1 or 2; the value of n is usually 1 or 2.
  • the atom of the metal ion Me n+ and/or the metal or metalloid oxide AO x it is possible to magnify the properties of the compound according to the invention, and a composition can be obtained having strong antibacterial, antiviral, antimycotic, microcide, photocatalytic, anti-pollution properties.
  • AO x may be for example titanium dioxide (Ti ⁇ 2) , zinc oxide (ZnO) , stannic oxide (Sn ⁇ 2) , zirconium dioxide (Zr ⁇ 2) , and colloidal silica (Si ⁇ 2) ; Me n+ may be chosen between transition metal ions.
  • ion Me n+ is chosen between Ag + and/or Cu ++ , i.e. metals having antibacterial, antimycotic, antiviral activity.
  • Bifunctional molecules L may be based on organic compounds.
  • Bifunctional molecules L may be organic or organometallic molecules, such as complexes of the transition metals.
  • the ligand L may be provided with different suitable functional groups, first functional group binding to the AO x oxide, and second functional group binding the Me n+ ions.
  • the first functional group may be chosen in a group comprising: carboxyl (-COOH) (or carboxylate) , phosphonic (-
  • the second functional group may be chosen in a group comprising: Cl “ , Br “ , I “ , S, SH, CNS “ , NH 2 , N, CN “ and NCS " .
  • said dipyridylic or terpyridylic group is substituted by a carboxyl group, more preferably in a para position with respect to the pyridine nitrogen.
  • the bifunctional ligands L can be selected in a group comprising: - nitrogen-containing heterocycles having 6 to 18 members, preferably pyridine, dipyridyl, or terpyridyl, possibly substituted with one or more substituents, selected preferably between: carboxyl (-COOH) , boronic
  • Ci8 aryls preferably selected from: phenyl, naphthyl, biphenyl, and possibly substituted with one or more substituents selected preferably between: carboxyl (-COOH) , boronic (-B(OH) 2 ), phosphonic (- PO 3 H 2 ), mercaptan (-SH), and hydroxyl (-0H);
  • Ci8 monocarboxylic and dicarboxylic acids possibly substituted with one or more mercaptan groups (-SH) and/or hydroxyl groups (-0H) .
  • pyridine, dipyridyl, or terpyridyl functionalized with carboxyl groups, boronic groups, or phosphonic groups; mercaptosuccinic acid, 11-mercaptoundecanoic acid, mercaptophenol, 6-mercaptonicotinic acid, 5- carboxypentanethiol, mercaptobutyric acid, and 4- mercaptophenylboronic acid.
  • the metal or metalloid oxides AO x are capable of adsorbing, by electrostatic or chemical interaction, such as via esteric bonds, to molecules having suitable functional groups, such as the following groups: carboxyl (-COOH) (or carboxylate) , phosphonic (-PO3H2) (or phosphonate) , or boronic (-B(OH) 2 ) (or boronate) , with which groups the bifunctional molecules L may be provided.
  • suitable functional groups such as the following groups: carboxyl (-COOH) (or carboxylate) , phosphonic (-PO3H2) (or phosphonate) , or boronic (-B(OH) 2 ) (or boronate) , with which groups the bifunctional molecules L may be provided.
  • each nanoparticle of AO x can be homogeneously covered by metal ions such as Ag + or Cu 2+ , and by fatty acid molecules as illustrated schematically by way of example in Figure 5.
  • metal oxide AO x comprises TiO 2 , preferably with Titanium in Anatase form, therefore an anti- pollution, photocatalytic composition can be obtained. Saturated and unsaturated fatty acids, having one or more double bonds may be efficiently used.
  • omega-3 fatty acid may be successfully used.
  • the fatty acid chains may reciprocally interact forming intermolecular linking promoting the homogeneous coverage of the treated surface by the product and the homogeneous spreading of the product on the treated surface.
  • different compounds differing by the particular fatty acid bound to a AO x nanoparticle may be present.
  • the compound of the product according to the invention may contain many different fatty acids.
  • AO x - (L-Me n+ ) x (FA) 3 different compounds differing by the real number of molecules of fatty acid bound to a AO x nanoparticle, may be present.
  • saturated fatty acids may be made to react with
  • AO x nanoparticle such as for example: Butyric acid
  • fatty acids with linear, or also branched chains may be used, and also fatty acids containing different functional group or groups, comprising, for example acetylenic bonds, epoxy- group/s, hydroxy- group/s, keto- group/s, and also ring functional group/s.
  • Alpha-linolenic acid, docosahexaenoic acid, and Eicosapentaenoic acids are examples of 0mega-3 fatty acids; Linoleic acid and arachidonic acid are 0mega-6 fatty acids; Oleic and erucic acid are omega-9 fatty acids.
  • omega-3 fatty acids ⁇ -Linolenic acid, Stearidonic acid, Eicosatetraenoic acid, Eicosapentaenoic acid, Docosapentaenoic acid, Docosahexaenoic acid (DHA) can be for example used.
  • the fatty acid molecule may comprise linoleic and/or oleic acids, known to exhibit an insecticidal effect, so as to further enhance the properties of the product.
  • a product having very limited dimensions i.e. a nano-compound
  • the product according to the invention may be dispersed in both in organic and in inorganic solvents, and also in hydrophilic and lipophilic solvents, obtaining very homogeneous suspensions.
  • the presence of the ligand L and of the metal ions Me n+ allows a good solvation in polar solvents to be obtained, whilst the fatty acid molecules FA allow a good solvation in non-polar solvents to be obtained.
  • Suitable additives may be added to the suspension of the product according to the invention, so as to obtain a product suitable to be applied to a desired substrate, for example a paint .
  • the product having general formula AO x - (L-Me n+ ) x (FA) 3 may be used for obtaining a paint, preferably a paint having lipophylic solvents.
  • (FA) 3 may be mixed to many desired substrate, for example to tissues, linking to the structure of the tissues and thus forming an antibacterial, antiviral tissue having a very homogeneous structure.
  • (FA) 3 may be mixed to plastics, so forming a plastic having a very homogeneous structure and antibacterial, antiviral properties .
  • the fatty acid molecules of the product forming stable bound with the molecules of the plastics.
  • the product having general formula AO x - (L-Me n+ ) x (FA) 3 may be mixed to products for topical use, such as creams, gels, night creams, lenitive creams or gels, moisturizing creams or gels, obtaining a topical-treatment product having antibacterial, antiviral, and curative properties.
  • a topical-treatment product efficacious for example against burns, irritations, inflammations, excoriations, and abrasions of the skin of a user may be obtained, or also a lenitive topical-treatment product, or also a cicatrizing topical-treatment product, may be obtained.
  • the product having general formula AO x - (L-Me n+ ) x (FA) 3 may be suitably mixed to any desired known topical- treatment product in form of a cream, gel, powder, microcapsule, efficaciously mixing to the known topical- treatment product.
  • the product having general formula AO x - (L-Me n+ ) ⁇ (FA) 3 may also be used for obtaining plant treating products.
  • the product having general formula AO x -(L-Me 1 ⁇ ) 1 (FA) 3 may also be applied in any desired way to any desired support, showing very good adhesion properties to many different supports and forming thereon very homogeneous films. Therefore, it is possible to confer to the desired support very homogeneous properties, in particular antibacterial, virucidal, insecticidal, photocatalytic properties.
  • the presence of the Ligand L molecules allow to bind the molecule of the metal ion Me n+ to the metal or metalloid oxide AO x .
  • the presence of the fatty acid molecules allow to bind the molecule of the metal or metalloid oxide AO x and also to enhance the adhesion properties of the product obtained to any desired substrate, in particular to a lipophylic substrate .
  • the fatty acid molecules enhance the compatibility of the product with many tissues, for example human tissues, or plant tissues, or also tissue having lipophylic functional groups, for example cellulose-based tissues.
  • the molecule of the fatty acids, and/or of the omega-3 acids are lipophilic molecules, the cells of the plants and, moreover, the cells of the dermal tissue of the plants, i.e. the outermost covering of a plant that is a outer single-layered group of cells covering a plant, especially the leaf and young tissues of a vascular plant including stems and roots, and the membranes thereof contain lipids and therefore are lipophilic too.
  • the product having general formula AO x - (L-Me n+ ) ⁇ (FA) 3 forms links with the cells of the leaves or of the particular area of the plants on which the products have been applied.
  • the afore mentioned links allow a stable adhesion of the product to the cells and/or tissues of the plants.
  • the fatty acid molecules enhance the compatibility of the product with plastics, or any other substrates having lipophylic functional groups.
  • the fatty acid molecules enhance the compatibility of the product with lipophylic solvents as, for example those used for obtaining paints.
  • the molecules of the fatty acid allow links with the cells of the lipophylic molecules of the substrate to be formed, therefore greatly enhancing the adhesion of the product thereon, and allowing the product to stably adhere to the substrate, so as to remain on the substrate for a considerable period pf time.
  • the product having general formula AO x - (L-Me n+ ) ⁇ (FA) 3 is not, thus, removed from a substrate on which it has been applied by the action of the raining, or by watering, or normal cleansing action.
  • Me n+ )i (FA) 3 it possible to treat the desired support in an environmental safe way, and causing no pollution to the environment .
  • the homogeneous mixing of the product to the substrate allows also any microorganism develop centre in the substrate to be avoided.
  • the products according to the first and second aspect of the invention comprise positively charged nanoparticles, and can give rise to suspensions in aqueous solvents or in polar solvents of an organic nature. Because of the broad spectrum of antibacterial action of materials containing silver and copper ions, the use of such materials as antibacterial, or antiviral, or biocide products is very effective.
  • Such nanomaterials may exhibit an antibacterial effect either in presence or in absence of light.
  • a method for treating a support comprising applying a product having general formula AO x - (L-Me n+ ) x (FA) 3 .
  • the support may be chosen form any desired support, for example a tissue, a cellulose tissue, a plant substrate, plastics.
  • an antibacterial, antiviral support By treating the desired support with the product having general formula AO x - (L-Me n+ ) x (FA) 3 , an antibacterial, antiviral support it is obtained. Moreover, a support is obtained having photocatalytic properties, and capable of destroying many polluting agents, both organic and inorganic, and many microorganisms. Moreover a intimate mixing and/or a homogeneous coverage of the desired support may be obtained, therefore, the above mentioned properties are very homogeneously spread in the support.
  • a method for killing microorganisms near a surface comprising applying a product containing at least a compound having general formula AO x -(L-Me 1 ⁇ ) 1 (FA) 3 .
  • a product containing at least a compound having general formula AO x -(L-Me 1 ⁇ ) 1 (FA) 3 it is provided for obtaining said product by preparing a suspension by mixing a solution comprising Titanium Dioxide nanoparticles with a further solution containing the ligand L and, therefore, with a still further solution containing at least one fatty acid FA.
  • a Titanium dioxide-based suspension in a rapid manner and in sufficient quantity to coat the surface that it is desired to treat without it being necessary to store the suspension, thus avoiding the risk that the suspension flocculates.
  • a product comprising a compound having general formula AO x - (L- Me ⁇ ) 1 (FA) 3 for killing at least organism chosen in a group comprising: bacteria, fungi, insects, mildews, sponges, viruses, algae, acaruses, mites, it is provided for.
  • a product comprising a compound having general formula AO x - (L- Me ⁇ ) 1 (FA) 3 for killing at least organism chosen in a group comprising: HSV-I (Herpes Simplex Virus-1), Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila, Pseudomonas aeruginosa, Staphylococcus aureus, Enterococcus faecalis, Escherica CoIi, Salmonella enteridis Dl, Listeria monocytogenes, Candida albicans, Aspergillus niger, Erwinia amilovora, Xanthomonas campestris.
  • HSV-I Herpes Simplex Virus-1
  • Poliovirus Poliovirus
  • Aviaria virus Legionella pneumophila
  • Pseudomonas aeruginosa Staphylococcus aureus
  • Enterococcus faecalis Enterococcus faecali
  • a paint comprising a compound having general formula AO x - (L-Me n+ ) x (FA) 3 is provided.
  • the paint further contains at least a solvent, preferably a lipophylic solvent.
  • a solvent preferably a lipophylic solvent.
  • Many different kinds of paint may be obtained, for example: varnish, lacquer, latex paint, enamel, fingerpaint, ink, anti-graphiti paint, anti-climb paint, lacquer, fresco paint.
  • transparent paints may also be obtained.
  • the paint may also comprise at least a pigment, and/or a dye, giving a colouring effect.
  • the paints may also contain binder means chosen in a group comprising: synthetic resins, natural resins, acrylics, polyurethanes, polyesters, melamines, epoxy, oils.
  • the paints may also contain filler means chosen in a group comprising: talc, clay, lime, baryte .
  • the paints may also contain diluent means, chosen in a group comprising: organic solvents, petroleum distillate, alcohols, ketones, esters, glycol ethers
  • the paints may also contain additive means chosen in a group comprising: pigments, dyes, catalysts, thickeners, stabilizers, emulsifiers, texturizers, adhesion promoting means, flatteners.
  • a topical treatment product comprising a compound having general formula AO x -(L-Me ⁇ ) 1 (FA) 3 is provided.
  • a tissues comprising a compound having general formula AO x - (L-Me n+ ) ⁇
  • a plastic comprising a compound having general formula AO x - (L-Me n+ ) ⁇ (FA) 3 is provided.
  • a substrate provided with coating means comprising a compound having general formula AO x - (L-Me n+ ) ⁇ (FA) 3 is provided.
  • a plant treating product comprising at least a compound having general formula Ti ⁇ 2 ⁇ (FA) 3 , wherein Ti ⁇ 2 indicates Titanium
  • the product comprises Titanium Dioxide nanoparticles comprised between about 10 and 5000 nm, fatty acid molecules comprised between about 10 ⁇ 2 % (w/w) and 5%
  • the product further comprises a surface-active agent comprised between about 0.1 % (w/v) and
  • the product comprises a colloidal suspension of Titanium Dioxide nanoparticles.
  • a method for preparing a plant treating product comprising mixing a solution containing Titanium Dioxide nanoparticles with a further solution containing at least one fatty acid.
  • said mixing comprises obtaining a compound having general formula Ti ⁇ 2 ⁇ (FA) 3 , wherein TiC>2 indicates Titanium Dioxide molecule, FA indicates a molecule of a fatty acid, and j is a parameter indicating the number of FA molecules bound to a Titanium Dioxide molecule.
  • the solution further contains methanol and/or ethanol as solvent.
  • the further solution further contains acetone as solvent.
  • the further solution contains the at least one fatty acid in an almost pure state.
  • mixing comprises stirring the solution and the further solution.
  • the plant treating product may be chosen in a group comprising biocides, products for promoting plant growth, insecticides, fungicides, pesticides, bactericides, etc.
  • the value of the parameter j may be comprised between about 100 and 10000.
  • the product containing the compound having general formula Ti ⁇ 2 ⁇ (FA) 3 may contain a very widely variable number of molecules of fatty acid linked to a molecule of Titanium Dioxide .
  • the real number of molecules of the fatty acid bound to a titanium dioxide nanoparticle, or AO x nanoparticle depends by the size of the nanoparticles and it can be calculated that, in the case of titanium dioxide nanocrystals having diameters of the order of 25-30 nm, at least 10-1000 fatty acid molecules, preferably 500-800 fatty acid molecules, can be organized and bound to the surface of each nanoparticle.
  • the number of fatty acid molecules which can be bound to the titanium dioxide nanocrystals depend also by the size of the fatty acid molecules used.
  • the fatty acid chains may reciprocally interact forming intermolecular linking promoting the homogeneous coverage of the treated surface by the product and the homogeneous spreading of the product on the treated surface.
  • different compounds having general formula TiO 2 -(FA) 3 differing by the real fatty acid bound to a titanium dioxide molecule, and/or the number of the molecule of the fatty acid bound to a single titanium dioxide molecule, may be present.
  • saturated fatty acids may be made to react with Titanium Dioxide nanoparticles, such as for example: Butyric acid (CH 3 (CH 2 ) 2 COOH) , Caproic acid (CH 3 (CH 2 ) 4COOH) , Caprylic acid (CH 3 (CH 2 ) 6 COOH) , Capric acid (CH 3 (CH 2 ) 8 COOH) , Erasmus acid (CH 3 (CH 2 ) I0 COOH), Myristic acid (CH 3 (CH 2 ) I2 COOH) , Palmitic acid (CH 3 (CH 2 ) 14 COOH) , Stearic acid (CH 3 (CH 2 ) I6 COOH) ,
  • unsaturated fatty acids that have a structure very similar to the structure of the saturated fatty acids, except that one, monounsaturated acids, or more, polyunsaturated acids, "double bonds", i.e, two carbon atoms reciprocally bound by a double bond, are present along the chain of such acids.
  • 0mega-3 fatty acids may also be used.
  • fatty acids with linear, or also branched chains may be used, and also fatty acids containing different functional group or groups, comprising, for example acetylenic bonds, epoxy- group/s, hydroxy- group/s, keto- group/s, and also ring functional group/s.
  • Isopalmitic acid, tuberculostearic acid, Phytomonic acid, Eicosapentaenoic acid, Docosahexaenoic acid, Erucic acid (CH 3 (CH 2 ) 7 CH CH(CH 2 ) 11 COOH) , Mycoceranic acid, Mycopelinic acid, Mycocerosic acid.
  • Alpha-linolenic acid, docosahexaenoic acid, and Eicosapentaenoic acids are examples of Omega-3 fatty acids; Linoleic acid and arachidonic acid are Omega-6 fatty acids; Oleic and erucic acid are omega-9 fatty acids.
  • omega-3 fatty acids ⁇ -Linolenic acid
  • Stearidonic acid Eicosatetraenoic acid
  • Eicosapentaenoic acid Eicosapentaenoic acid
  • Docosapentaenoic acid Docosahexaenoic acid (DHA)
  • DHA Docosahexaenoic acid
  • the product according to the twelfth and thirteenth aspect of the invention may comprise a plant growth promoting product.
  • oxides of many metallic or non-metallic elements such as, for example, of Li, Be, B, Na, Mg, Co, Ni, cu, P, K, Al, Si, Ca, Sc, V, Cr, Mn, Fe, Zn, Ga, Ge, Se, Zr, or a mixture thereof may be added for further promoting plant growth.
  • Such elements may be absorbed by the plants, thus promoting the growth thereof.
  • a product may be used for a very wide range of plant type, for example, fruit trees, cereal cultures, rice plants, corn plants, wheat plants, maize plants, tomato, potato, etc.
  • the content of the afore mentioned metallic or non-metallic oxides may be comprised between about 0.1% to 25% by weight, preferably between about 0.5% to 20%, further preferably between about 5% to 10%, by weight in respect to the quantity of the Titanium dioxide. Linoleic and oleic acids, known to exhibit an insecticidal effect, may also be used for obtaining the compound having general formula Ti ⁇ 2 ⁇ (FA) 3 .
  • the molecules of the fatty acids such as linoleic and oleic acids being bound to the molecule of the Titanium Dioxide.
  • the properties of the fatty acid/s present in the compound having general formula TiC>2- (FA) 3 add to the properties of the other molecules of the compound, mostly to the properties of the Titanium, thus magnifying the properties of the product obtained.
  • the insecticidal properties of the linoleic and/or oleic acid are added to the properties of the Titanium Dioxide, therefore the product obtained has magnified and highly intensified properties and efficacy.
  • a method for treating plant comprising applying a product containing at least a compound having general formula Ti ⁇ 2 ⁇
  • FA (FA) 3 , wherein TiC>2 indicates Titanium Dioxide molecule, FA indicates a molecule of a fatty acid, and j is a parameter indicating the number of FA molecules bound to a Titanium Dioxide molecule.
  • a method for killing microorganisms near a surface of a plant comprising applying a product containing at least a compound having general formula Ti ⁇ 2 ⁇ (FA) 3 , wherein Ti ⁇ 2 indicates Titanium Dioxide molecule, FA indicates a molecule of a fatty acid, and j is a parameter indicating the number of FA molecules bound to a Titanium Dioxide molecule.
  • a method for eliminating polluting substances near a surface of a plant comprising applying a product comprising at least a compound having general formula Ti ⁇ 2 ⁇ (FA) 3 , wherein TiC>2 indicates Titanium Dioxide molecule, FA indicates a molecule of a fatty acid, and j is a parameter indicating the number of FA molecules bound to a Titanium Dioxide molecule.
  • a plant treating product comprising a compound having general formula Ti ⁇ 2 - (FA) 3 for killing at least organism chosen in a group comprising: bacteria, fungi, insects, mildews, sponges, viruses, algae, acaruses, mites, it is provided for.
  • a plant treating product comprising a compound having general formula Ti ⁇ 2- (FA) 3 as pesticide, and/or antimycotic, and/or insecticides, and/or algicide, and/or moluscicide, and/or miticide, and/or rodenticide, and/or antimicrobial, and/or germicide, and/or antibacterial, and/or antiviral, and/or antifungal, and/or antiprotoas, and/or antiparasite, and/or preservative, and/or biocide, and/or plant growth promoting, and/or anti-polluting, and/or photocatalytic product, it is provided for.
  • the products according to the invention have very good adhesion properties, in particular such a product once applied on a plant or on any other vegetable substrate durably and stably adhere thereto.
  • the molecule of the fatty acids, and/or of the omega-3 acids are lipophilic molecules, the cells of the plants and, moreover, the cells of the dermal tissue of the plants, i.e. the outermost covering of a plant that is a outer single-layered group of cells covering a plant, especially the leaf and young tissues of a vascular plant including stems and roots, and the membranes thereof contain lipids and therefore are lipophilic too.
  • the plant treating product according to the invention forms links with the cells of the leaves or of the particular area of the plants on which the products have been applied.
  • the afore mentioned links allow a stable adhesion of the plant treating product according to the invention to the cells and/or tissues of the plants.
  • the plant treating product according to the invention is not removed from a plant on which it has been applied by the action of the raining, or by watering.
  • the action of the plant treating product according to the invention may be exerted on a plant on which it has been applied for a prolonged interval of time.
  • a plant treating product according to the invention may be applied less frequently.
  • Tests have shown that a plant treating product according to the invention may be applied every three months on a plant. Moreover tests have also shown that during the interval of time comprised between two consecutive applications, the plant treating product maintains a good efficacy exerting its own properties on the treated plant. This implies that less frequent interventions by the farmer, or by the cultivators, are necessary, with consequent considerably money and time savings.
  • the molecules of the plant treating product according to the invention have very limited dimensions, therefore such a product may very homogeneously cover a desired surface, thus forming on such a surface a very homogeneous film that protects almost all the treated surface . Therefore, the protection conferred by the plant treating product according to the invention to a surface treated therewith extends almost on all the extension of the treated surface . The presence of nuclei of microorganisms development and/or growth in a plant treated with a product according to the invention is thus avoided.
  • the molecules of the fatty acid of the different molecules of a plant treating product according to the invention may reciprocally interact forming intermolecular linking.
  • a method for treating plant that is environmental safe and does not cause any pollution to the environment is obtained. Moreover, it is obtained a plant treating product that covers almost homogeneously the surface of the plant to which it is applied, therefore removing almost completely any bacteria, or insects, or any other microorganisms present on such surface, and avoiding almost completely any subsequent proliferation thereof.
  • Such a product may be stably adhered to the substrate to which it is applied.
  • Ramsewak, R. S., et al . J. Agric Food Chem 2001, 49, 5852
  • linoleic and oleic acids were insecticidal against Aedes aegvptii larvae and exhibited potent feeding deterrent activity against neonate larvae of Helicoverpa zea, Limantria dispar, Orgyia leucostigma and Malacosoma disstria.
  • a plant treating product that is very efficacious for removing microorganisms such as, for example Pseudomonas, Erwinia amilovora, Xanthomonas campestris, fungi, from plants, flowers, trees.
  • microorganisms for example Erwinia amilovora
  • Many microorganisms are very harmful for many various plants, which are affected by a certain pathogenic agent suddenly wither and die.
  • microorganisms spread very easily and in very short period of time between different plants thus spreading the contagion to many plants.
  • Erwinia amilovora causes diseases known as "fire blight" that is one of the most destructive diseases of apple and pear, causing extensive tree damage when outbreaks do occur.
  • Epidemics develop quickly, destroying blossoms, vegetative shoots, major limbs and, sometimes, whole trees. Erwinia amylovora overwinters in cankers on infected limbs. Cankers become active in early spring as temperatures warm and buds begin to develop. Active cankers produce a yellowish to white bacterial ooze that can appear several weeks prior to bloom. During this period, insects (mainly flies) disseminate the bacteria throughout the orchard. During bloom, pollinating insects rapidly move the pathogen from flower to flower initiating the blossom blight phase of the disease. Flowers can become infected within minutes after a rain or heavy dew.
  • Inoculum produced from infected blossoms is further spread by wind, rain, and insects. Treating a plant affected and infected by Erwinia Amylovora a product according to the invention, allows eliminating very easily, and in a very fast manner the microorganism infecting the plant, as will be better discussed in the followings with reference to the drawings. A further spreading or proliferation of the microorganism is also completely avoided.
  • the products according to the invention are also a non- polluting plant treating product that can be used in agriculture without any limitation due to the environmental laws .
  • the plant treating product according to the invention may be chosen in a group comprising: pesticides, antimycotics, herbicides, insecticides, algicides, moluscicides, miticides, rodenticides, antimicrobial products, germicides, antibiotics, antibacterials, antivirals, antifungals, antiprotoas, antiparasites, preservatives, plant growth promoting products.
  • the photocatalytic reactions carried out by the Titanium Dioxide nanoparticles may result in an increase of the carbon Dioxide concentration, which is one of the products obtained by the photocatalytic oxidative reactions, near the Titanium Dioxide nanoparticles, i.e. near the surface of the plant on which the product according to the invention has been applied.
  • Titanium Dioxide nanoparticles of the plant treating product according to the invention may be both in the form of Brookite, and/or Rutile, and/or Anatase, and/or a mixture thereof .
  • the molecules of the fatty acid bound to the Titanium Dioxide nanoparticles may be of the same fatty acid, or also many different fatty acids may be bound to a Titanium Dioxide nanoparticles .
  • the products according to the invention show very good adhesion properties, in particular such a product may be successfully applied on plant or any other vegetable substrate and firmly adhere thereto.
  • Figures 1 to 3 are frontal views of bacterial cultures of Erwinia Amylovora treated with products for treating plants according to the invention having different values of the concentration of Titanium Dioxide;
  • Figure 4 is a schematic representation of a molecule of the plant treating product having general formula TiC>2 (FA) 3 according to the invention
  • Figure 5 is a schematic representation of a molecule of the nanoparticle having general formula AO x -(L-Me ⁇ ) 1 (FA) 3 according to the invention.
  • Titanium Dioxide is a semiconductor material with a crystalline structure, having a valence band separated from a conduction band by a given energy difference.
  • Solid-state Titanium Dioxide has tree allotropic forms named Anatase, Rutile, and Brookite. Titanium Dioxide in any of the afore mentioned forms and in particular those of Anatase and, in part of Rutile, has photocatalytic, antibacterial, virucidal, fungicidal, properties .
  • Some of the Titanium Dioxide based compounds show the afore mentioned properties if irradiated by light, for example solar irradiation, or light from another desired energy source, for example a source of ultraviolet (UV) radiation, such as an ultraviolet ray lamp.
  • UV radiation ultraviolet
  • the Anatase form of the Titanium Dioxide is the most active crystalline form from the photocatalytic point of view.
  • the energy difference between the valence band and the conduction band is for the Anatase form of the Titanium Dioxide of 3.2 eV and that of Rutile is 3.0 eV.
  • a material is composed by a mixture of Anatase and Rutile it can absorb photons with a wavelength equal or shorter than ca 420 nm.
  • an electromagnetic radiation having a wavelength equal or lower than 420 nm, electrons are caused to pass from the valence band, at lower energy, to the conduction band, at higher energy. This occurs in particular when the Titanium Dioxide is hit by the solar radiation, since photons emitted by the sun in the wavelength range from 360 nm to 420 nm can easily reach the earth surface.
  • the positive charges are strong oxidizing agents, with a potential of the order of + 2.6 eV vs. the normal hydrogen electrode, and can oxidize most organic contaminants.
  • Such electronic holes can, for example, react with hydroxyl groups covering the surface of the semiconductor or with molecules of water (H 2 O) present in the atmosphere generating hydroxyl radicals ( * OH) which are highly reactive species .
  • the excess electrons have a reducing power from -0.4 to -0.6 eV which is sufficient to generate the superoxide anion (02 * ) by reaction with oxygen molecules.
  • the hydroxyl radical ( ' 0H) is particularly active both for the oxidation of organic and inorganic substances, for example present in the air, as well as for deactivating microorganisms, that may, for example be harmful to cultivated plants and people.
  • the organic compounds are oxidized to carbon Dioxide (CO 2 ) and water (H 2 O)
  • the nitrogen compounds are oxidized to nitrate ions (N ⁇ 3 ⁇ )
  • the sulphur compounds are oxidized to sulphate ions (SO 4 2- ) .
  • Titanium Dioxide is furthermore able to decompose many gases or harmful substances such as thiols or mercaptans, formaldehyde, having an unpleasant smell.
  • gases or harmful substances such as thiols or mercaptans, formaldehyde, having an unpleasant smell.
  • the decomposition of such gases or substances eliminates the bad smells associated therewith.
  • Titanium Dioxide furthermore has an antimicrobial, antibacterial, antiviral, fungicide, anti-mould action that is very effective. Tests have been conducted on the growth of microorganisms in the presence and absence of a plant treating product according to the invention.
  • Dioxide namely a first product containing approximately
  • the tests were conducted by applying to each culture the three afore mentioned different products with different concentrations Titanium Dioxide and comparing the development of the microorganisms of Erwinia Amylovora with a control plate containing only the microorganisms culture.
  • the cultures were exposed to light irradiation for an average period of 12 hours by using a lamp that simulates the solar spectrum as well as under solar light conditions for a comparable period of time.
  • the light source was placed at a distance comprised between approximately 60 cm and 70 cm from the plates in which the microorganisms were cultivated.
  • the infrared radiation, responsible of overheating, was cut off with water filters.
  • Water cut off filters were also used in the outdoor experiments under sun light irradiation. At the end of the experiments, after 12 h of irradiation, constant aliquots of the liquid terrains were taken from each plate and sowed in an agar terrain to determine the number of survived bacteria. The sowed plates were kept at 37 °C for 24 hours and the developed colonies then counted.
  • a plate is shown corresponding to the treatment with a product having a concentration of Titanium Dioxide of 0.025% w/v, that causes a considerably reduction in the number of colonies of Erwinia Amylovora, but that is not sufficient to cause the mortality of all the colonies of Erwinia Amylovora, about 650 colonies may be counted.
  • FIG 3 shows a plate corresponding to the treatment with a product having a concentration of Titanium Dioxide of
  • Titanium Dioxide and/or Ag + and/or Cu ++ ions.
  • Table 1 are reported the results obtained in analogous experiments performed with a compound having general formula Ti ⁇ 2 ⁇ (FA) 3 in the presence of different microorganism, including the bacteria Erwinia Amylovora, Pseudomonas Aeruginosa, Escherichia CoIi, Staphilococcus Aureus, and the fungus Candida Albicans.
  • an antibacterial, antiviral, antifungal agent such as, for example Titanium Dioxide, and/or Ag + and/or Cu ++ ions.
  • Dioxide allow a considerable reduction of the number of colonies of the different microorganisms on which experiments have been conducted.
  • Titanium Dioxide causes a complete mortality of the colonies of Escherica Colii, whilst a concentration of 0.125% (w/v) of
  • Titanium Dioxide is sufficient to cause a complete mortality of the colonies of Staphylococcus Aureus and also of Erwinia
  • the molecule M comprises a Titanium Dioxide nanoparticle 1 to which a plurality of fatty acids molecules 2 is bound.
  • Each fatty acids molecule 2 is so oriented that the carboxylic functional group 2a of the molecule of the fatty acid is bound to the Titanium Dioxide nanoparticle 1.
  • Titanium Dioxide nanoparticle 1 can be chosen by suitably varying the preparation conditions.
  • the number of fatty acid molecules 2 which can be adsorbed on the surface of a nanoparticle having a diameter of the order of 30 nm is comprised in the range between 10 and
  • the adhesion properties of the semiconductor nanoparticles on lipophylic surfaces increases by increasing the number of fatty acid molecules adsorbed on their surface.
  • Titanium Dioxide nanoparticles 1 it is possible to bound the Titanium Dioxide nanoparticles 1 to molecules of many different fatty acids, so obtaining different plant treating products that can be used for many different purposes. Moreover, it is possible to bound a single Titanium Dioxide nanoparticle 1 to the molecules 2 of different fatty acids.
  • products for treating plants may be obtained containing different kind of molecule M, i.e. molecule in which the Titanium Dioxide nanoparticles are bound to many different fatty acids that vary from a molecule M to another .
  • the molecule Ml comprises a AO x nanoparticle 10 to which a plurality of fatty acids FA molecules 20 are bound.
  • Each fatty acids molecule 20 is so oriented that the carboxylic functional group 21 of the molecule of the fatty acid 20 is bound to the AO x nanoparticle 10.
  • the number of the fatty acids molecules 20 bound to each AO x e nanoparticle 10 can be chosen by suitably varying the preparation conditions.
  • the number of fatty acid molecules 20 which can be adsorbed on the surface of a nanoparticle having a diameter of the order of 30 nm is comprised in the range between 10 and 1000, preferably between about 500 and 800.
  • products having a molecular weight varying in a very wide range of values may be obtained.
  • products having very different physical properties may also be obtained.
  • the adhesion properties of the semiconductor nanparticles on lipophylic surfaces increases by increasing the number of fatty acid molecules adsorbed on their surface.
  • the AO x nanoparticles 10 it is possible to bound the AO x nanoparticles 10 to molecules of many different fatty acids, so obtaining different products that can be used for many different purposes . Moreover, it is possible to bound a single AO x nanoparticle 10 to the molecules 20 of different fatty acids. Furthermore, products may be obtained containing different kind of molecules Ml, i.e. molecules in which the AO x nanoparticles are bound to many different fatty acids that vary from a molecule Ml to another.
  • the molecule Ml further comprises bifunctional ligand L molecules 30 bound to the AO x nanoparticles 10.
  • the number of the ligand molecules 30 depending on various factors such as the specific ligand used, the preparation conditions, etc.
  • Each ligand molecule 30 is interposed between a AO x nanoparticle 10 and a metal ion 40 Me + .
  • the number of metal ions 40 bound to the AO x nanoparticle 10 via the ligand molecules 30 depends on many different factors .
  • the ligand molecules 30, together with the metal ions 40 Me + are bound to the AO x nanoparticle 10 and are arranged so that almost all the surface of the AO x nanoparticle is covered by ligand L and, therefore by ions Me + .
  • Example 1 Production of suspensions of nanomaterials having antibacterial and antiviral activity
  • a first stage of adsorption is carried out wherein the bifunctional ligand L is adsorbed, followed by mixing with an aqueous or alcoholic solution containing Ag + or Cu 2+ ions.
  • adsorption of the bifunctional ligand L onto a nanomaterial AO x described in the present invention requires times on the order of 12-48 hr, whereas the bonding of Ag + or Cu 2+ ions to the ligand L is stabilized nearly instantly by addition of solutions containing these ions to the suspensions of the nanomaterials functionalized with the ligand L.
  • the fatty acid molecules can be then bound to the AO x - (L- Me n+ )i functional nanomaterial by addition of solutions containing the fatty acid molecules to the suspensions of AO x -(L-Me 1 ⁇ ) 1 .
  • Example 2 Adsorption of 4-mercaptophenylboronic acid and Ag- ions or Cu- and oleic acid onto "TiO 2 P25" (supplied by Degussa)
  • Example 4 Coating TiO 2 with Stearic acid
  • the solid was washed with two 10 ml portions of acetone and dried at 40 0 C.
  • Adsorption of Omega-3 fatty acids on Titanium Dioxide nanoparticles was performed by stirring overnight 1.000 g of TiO 2 in 40 ml of an acetone solution containing 1.0 ml of Omega-3 fatty acids, such as for example ⁇ -linolenic acid (abbreviated as ALA, chemical formula CiSH 30 O 2 ) , Stearidonic acid (chemical formula CiSH 28 O 2 ) , Eicosapentaenoic acid (chemical formula C20H30O2, abbreviated as EPA) ,
  • Omega-3 fatty acids such as for example ⁇ -linolenic acid (abbreviated as ALA, chemical formula CiSH 30 O 2 ) , Stearidonic acid (chemical formula CiSH 28 O 2 ) , Eicosapentaenoic acid (chemical formula C20H30O2, abbreviated as EPA) ,
  • EPA ⁇ -linolenic acid
  • Docosahexaenoic acid (chemical formula C22H32O2, commonly known as DHA)
  • Docosapentaenoic acid chemical formula C 22 H 34 O 2 .
  • Example 6 Adsorption of Whyley acid on TiO 2
  • LrCOOH Chemical formula CH 3 (CH 2 ) I 0 COOH
  • TiO 2 Adsorption of Laurie acid (abbreviated as LrCOOH, chemical formula CH 3 (CH 2 ) I 0 COOH) on Titanium Dioxide nanoparticles, was performed by stirring overnight 1.000 g of TiO 2 in 20 ml of an acetone solution containing 1.00 g of LrCOOH. The solid was then washed with two 10 ml portions of acetone and dried at 40 0 C. Analysis performed on the solid sample shown that 140 mg of LrCOOH were adsorbed on 1.000 g of TiO 2 .
  • Example 7 Adsorption of Myristic acid on TiO 2
  • Adsorption of Myristic acid (chemical formula Ci 4 H 28 O 2 , abbreviated as MrCOOH) on Titanium Dioxide nanoparticles was performed by stirring overnight 1.000 g of TiO 2 in 20 ml of an acetone solution containing 1.00 g of MrCOOH. The solid obtained was then washed with two 10 ml portions of acetone and, therefore dried at 40 0 C. The solid has been therefore analysed and the analysis shows that 110 mg of MrCOOH were adsorbed on 1.000 g of TiO 2 .
  • Example 8 Adsorption of Palmitic acid on TiO 2
  • Palmitic acid (chemical formula Ci6H 32 O 2 , abbreviated as PmCOOH) has been adsorbed on Titanium Dioxide nanoparticles by stirring overnight 1.000 g of TiO 2 in 20 ml of an acetone solution containing 1.00 g of PmCOOH.
  • Example 9 Adsorption of Behenic acid on TiO 2
  • BnCOOH chemical formula C 22 H 44 O 2
  • TiO z was performed by stirring overnight 1.000 g of TiO z in 20 ml of an acetone solution containing 1.00 g of BnCOOH.
  • the solid was washed with two 10 ml portions of acetone and dried at 40 0 C.
  • Titanium Dioxide nanoparticles as, for example those previously listed.
  • ingredients may be added to the plant treating product according to the invention, so as to obtain different products that can be used for many different uses, and in many different forms.
  • the plant treating product according to the invention contains between about 0.01% (w/v) and 0.3% (w/v) of Titanium Dioxide.
  • the plant treating product according to the invention contains between about 10 ⁇ 2 % (w/w) and 5% (w/w) of fatty acids with respect to the amount TiO 2 .
  • the plant treating product according to the invention may be distributed in the form of film on plant surfaces, plants, crops, and it is suitable for being distributed by means of spray techniques, or by means of techniques that provide for spreading a film on the surfaces to be treated.
  • the plant treating product according to the invention remains substantially unaltered in a temperature range comprised between approximately 10 0 C and approximately 120°C. This temperature range enables the plant treating product according to the invention to be used for treating plants growing in many different environmental condition and subjected to a very wide range of environmental temperatures.
  • the plant treating product according to the invention may be used for treating both plants subjected to tropical climate, and polar climate.
  • the plant treating product according to the invention allows eliminate very effectively any microorganisms infesting and/or affecting a treated plant, and avoid any subsequent growing of such a microorganism, denature bacterial strains or fungi that are particularly harmful for agriculture and also allows polluting agents in the atmospheric air to be removed.
  • Titanium Dioxide used may be chosen amongst any available form of the Titanium Dioxide, preferably Titanium Dioxide used comprises approximately 80% Anatase and approximately 20% Rutile, with a density from approximately 3.6 g/cm 3 to approximately 3.9 g/cm 3 and a surface area from approximately 52 m 2 /g to approximately 56 m 2 /g.
  • the Titanium Dioxide furthermore has an average dimension of particles from approximately 25 nm to approximately 30 nm and a granulometric distribution that may vary in the range from approximately 5 nm to approximately 50 nm.
  • Titanium Dioxide may be of the type commercially known as Degussa P 25.
  • the surface-active agent also known as a surfactant, may be chosen between a glycol, or a polyethylene glycol, or a polyethylene glycol-phenyl-ether, or a polyethylene-glycol- ether, or a polyoxyethylene-stearyl-ether, or a polyethylene-glycol-hexadecyl-ether, or a polyethylene- glycol-octadecyl-ether, or a polyethylene-glycol-dodecyl- ether .
  • the surface-active agent can be chosen from a group of non-ionic surfactants comprising: Triton X-45, Triton X-IOO, Triton X-114, Triton X-165, Triton X-305, Triton X-405, Triton X-705-70, Triton CFlO, Brij 30, Brij 35 P, Brij 52, Brij 56, Brij 58 P, Brij 72, Brij 76, Brij 78 P, Brij 92V, Brij 96 V.
  • the surfactants act as stabilisers of the plant treating product and enable the product to be distributed evenly on any plant substrate.
  • Triton X 100 is the surfactant that is particularly indicated for agricultural use, since it is known that such a surfactant does not cause undesired effects in the human organism.

Abstract

La présente invention concerne un produit contenant un composé de type nanomatériau, de formule générale AOx-(L-Men+) i (FA) j, où AOx est un oxyde métallique ou métalloïde dans lequel x indique le nombre d'atome(s) d'oxygène (O) lié(s) à l'atome métallique (A) ; Men+ est un ion métallique ; L représente une molécule bifonctionnelle susceptible de se lier tant à l'oxyde métallique ou à l'oxyde métalloïde (AOx) qu'à l'ion métallique (Men+), i est un paramètre indiquant le nombre de groupes (L-Men+) liés à l'oxyde métallique AOx, (FA) est une molécule d'acide gras liée aux nanoparticules de AOx, j correspond à un autre paramètre indiquant le nombre de molécules d'acide gras (FA) liées à une nanoparticule de AOx.
PCT/EP2007/054452 2007-05-08 2007-05-08 Produits comprenant une composition anti-microbienne à base de nanoparticules de dioxyde de titane WO2008135093A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2007/054452 WO2008135093A1 (fr) 2007-05-08 2007-05-08 Produits comprenant une composition anti-microbienne à base de nanoparticules de dioxyde de titane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2007/054452 WO2008135093A1 (fr) 2007-05-08 2007-05-08 Produits comprenant une composition anti-microbienne à base de nanoparticules de dioxyde de titane

Publications (1)

Publication Number Publication Date
WO2008135093A1 true WO2008135093A1 (fr) 2008-11-13

Family

ID=38973154

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/054452 WO2008135093A1 (fr) 2007-05-08 2007-05-08 Produits comprenant une composition anti-microbienne à base de nanoparticules de dioxyde de titane

Country Status (1)

Country Link
WO (1) WO2008135093A1 (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010079037A2 (fr) * 2008-12-18 2010-07-15 Basf Se Dispersion aqueuse contenant des particules de pesticides et un amphiphile
EP2456305A2 (fr) * 2009-07-21 2012-05-30 Marrone Bio Innovations, Inc. Utilisation de la sarmentine et de ses analogues dans la lutte contre les parasites des plantes
CN102578149A (zh) * 2012-01-14 2012-07-18 哈尔滨工程大学 一种磁性杀菌材料及其制备方法和应用方法
WO2012151407A1 (fr) * 2011-05-04 2012-11-08 Averett Stewart Benson Compositions photocatalytiques à base de dioxyde de titane et leurs utilisations
CN102948432A (zh) * 2012-09-21 2013-03-06 田福祯 一种中草药纳米载银二氧化钛空气净化剂及其制备方法
US9642209B2 (en) 2009-10-08 2017-05-02 Delos Living, Llc LED lighting system
US9715242B2 (en) 2012-08-28 2017-07-25 Delos Living Llc Systems, methods and articles for enhancing wellness associated with habitable environments
US9832996B2 (en) 2013-10-01 2017-12-05 Marrone Bio Innovations, Inc. Use of sarmentine and its analogues with an herbicide, and compositions thereof
CN108522538A (zh) * 2017-03-01 2018-09-14 浙江源程环保科技有限公司 一种水体消毒剂
US10434203B2 (en) 2014-06-23 2019-10-08 WELL Shield LLC Reduction of infections in healthcare settings using photocatalytic compositions
US10599116B2 (en) 2014-02-28 2020-03-24 Delos Living Llc Methods for enhancing wellness associated with habitable environments
CN112262855A (zh) * 2020-10-28 2021-01-26 湖北省烟草科学研究院 一种防治烟草青枯病的方法及NaHS在防治烟草青枯病菌中的应用
US10923226B2 (en) 2015-01-13 2021-02-16 Delos Living Llc Systems, methods and articles for monitoring and enhancing human wellness
US11338107B2 (en) 2016-08-24 2022-05-24 Delos Living Llc Systems, methods and articles for enhancing wellness associated with habitable environments
IT202100022595A1 (it) * 2021-08-31 2023-03-03 Ntc S R L Composto in forma di particelle funzionalizzate con metallo ionico ad alta percentuale, e suo uso come antimicrobico
US11649977B2 (en) 2018-09-14 2023-05-16 Delos Living Llc Systems and methods for air remediation
US11668481B2 (en) 2017-08-30 2023-06-06 Delos Living Llc Systems, methods and articles for assessing and/or improving health and well-being
US11844163B2 (en) 2019-02-26 2023-12-12 Delos Living Llc Method and apparatus for lighting in an office environment
US11898898B2 (en) 2019-03-25 2024-02-13 Delos Living Llc Systems and methods for acoustic monitoring

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050084464A1 (en) * 2003-10-16 2005-04-21 Kimberly-Clark Worldwide, Inc. Method for reducing odor using metal-modified particles
WO2005060610A2 (fr) * 2003-12-11 2005-07-07 The Trustees Of Columbia University In The City Ofnew York Particules a taille nanometrique, leurs procedes d'obtention, compositions et leurs utilisations
CN1676227A (zh) * 2005-04-28 2005-10-05 湖南泰鑫瓷业有限公司 纳米TiO2载银抗菌薄膜的制造方法
WO2006125496A2 (fr) * 2005-05-26 2006-11-30 Flamma S.P.A. Formulations pharmaceutiques renfermant des principes actifs pharmaceutiques absorbes sur des nanoparticules de dioxyde de titane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050084464A1 (en) * 2003-10-16 2005-04-21 Kimberly-Clark Worldwide, Inc. Method for reducing odor using metal-modified particles
WO2005060610A2 (fr) * 2003-12-11 2005-07-07 The Trustees Of Columbia University In The City Ofnew York Particules a taille nanometrique, leurs procedes d'obtention, compositions et leurs utilisations
CN1676227A (zh) * 2005-04-28 2005-10-05 湖南泰鑫瓷业有限公司 纳米TiO2载银抗菌薄膜的制造方法
WO2006125496A2 (fr) * 2005-05-26 2006-11-30 Flamma S.P.A. Formulations pharmaceutiques renfermant des principes actifs pharmaceutiques absorbes sur des nanoparticules de dioxyde de titane

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; LIU, GUO-CONG ET AL: "Studies on adsorption and photodegradation of pesticide by Pd/TiO2 nanopowder with quartz crystal microbalance", XP002467481, retrieved from STN Database accession no. 2007:777361 *
DATABASE WPI Week 200615, Derwent World Patents Index; AN 2006-137762, XP002467482 *
FENXI CESHI XUEBAO , 26(3), 300-304 CODEN: FCEXES; ISSN: 1004-4957, 2007 *

Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010079037A3 (fr) * 2008-12-18 2011-05-12 Basf Se Dispersion aqueuse contenant des particules de pesticides et un amphiphile
JP2012512825A (ja) * 2008-12-18 2012-06-07 ビーエーエスエフ ソシエタス・ヨーロピア 農薬粒子と両親媒性物質とを含む水性分散液
WO2010079037A2 (fr) * 2008-12-18 2010-07-15 Basf Se Dispersion aqueuse contenant des particules de pesticides et un amphiphile
US9179675B2 (en) 2009-07-21 2015-11-10 Marrone Bio Innovations, Inc. Use of sarmentine and its analogs for controlling plant pests
EP2456305A2 (fr) * 2009-07-21 2012-05-30 Marrone Bio Innovations, Inc. Utilisation de la sarmentine et de ses analogues dans la lutte contre les parasites des plantes
EP2456305A4 (fr) * 2009-07-21 2013-01-02 Marrone Bio Innovations Inc Utilisation de la sarmentine et de ses analogues dans la lutte contre les parasites des plantes
US8466192B2 (en) 2009-07-21 2013-06-18 Marrone Bio Innovations, Inc. Use of sarmentine and its analogs for controlling plant pests
US8957000B2 (en) 2009-07-21 2015-02-17 Marrone Bio Innovations, Inc. Use of sarmentine and its analogs for controlling plant pests
US11109466B2 (en) 2009-10-08 2021-08-31 Delos Living Llc LED lighting system
US10952297B2 (en) 2009-10-08 2021-03-16 Delos Living Llc LED lighting system and method therefor
US10477640B2 (en) 2009-10-08 2019-11-12 Delos Living Llc LED lighting system
US9642209B2 (en) 2009-10-08 2017-05-02 Delos Living, Llc LED lighting system
US9833003B2 (en) 2011-05-04 2017-12-05 WELL Shield LLC Titanium dioxide photocatalytic compositions and uses thereof
US9144242B2 (en) 2011-05-04 2015-09-29 Stewart Benson Averett Titanium dioxide photocatalytic compositions and uses thereof
US9055751B2 (en) 2011-05-04 2015-06-16 WELL Shield LLC Titanium dioxide photocatalytic compositions and uses thereof
US9392795B2 (en) 2011-05-04 2016-07-19 WELL Shield LLC Titanium dioxide photocatalytic compositions and uses thereof
US9402400B2 (en) 2011-05-04 2016-08-02 Stewart Benson Averett Titanium dioxide photocatalytic compositions and uses thereof
CN103608108A (zh) * 2011-05-04 2014-02-26 斯图尔特·本森·阿沃雷特 二氧化钛光催化剂组合物及其应用
WO2012151407A1 (fr) * 2011-05-04 2012-11-08 Averett Stewart Benson Compositions photocatalytiques à base de dioxyde de titane et leurs utilisations
US8609121B2 (en) 2011-05-04 2013-12-17 Stewart B. Averett Titanium dioxide photocatalytic compositions and uses thereof
CN102578149A (zh) * 2012-01-14 2012-07-18 哈尔滨工程大学 一种磁性杀菌材料及其制备方法和应用方法
US10845829B2 (en) 2012-08-28 2020-11-24 Delos Living Llc Systems, methods and articles for enhancing wellness associated with habitable environments
US11587673B2 (en) 2012-08-28 2023-02-21 Delos Living Llc Systems, methods and articles for enhancing wellness associated with habitable environments
US10691148B2 (en) 2012-08-28 2020-06-23 Delos Living Llc Systems, methods and articles for enhancing wellness associated with habitable environments
US10928842B2 (en) 2012-08-28 2021-02-23 Delos Living Llc Systems and methods for enhancing wellness associated with habitable environments
US9715242B2 (en) 2012-08-28 2017-07-25 Delos Living Llc Systems, methods and articles for enhancing wellness associated with habitable environments
CN102948432A (zh) * 2012-09-21 2013-03-06 田福祯 一种中草药纳米载银二氧化钛空气净化剂及其制备方法
US9832996B2 (en) 2013-10-01 2017-12-05 Marrone Bio Innovations, Inc. Use of sarmentine and its analogues with an herbicide, and compositions thereof
US10599116B2 (en) 2014-02-28 2020-03-24 Delos Living Llc Methods for enhancing wellness associated with habitable environments
US10712722B2 (en) 2014-02-28 2020-07-14 Delos Living Llc Systems and articles for enhancing wellness associated with habitable environments
US11763401B2 (en) 2014-02-28 2023-09-19 Delos Living Llc Systems, methods and articles for enhancing wellness associated with habitable environments
US10434203B2 (en) 2014-06-23 2019-10-08 WELL Shield LLC Reduction of infections in healthcare settings using photocatalytic compositions
US10923226B2 (en) 2015-01-13 2021-02-16 Delos Living Llc Systems, methods and articles for monitoring and enhancing human wellness
US11338107B2 (en) 2016-08-24 2022-05-24 Delos Living Llc Systems, methods and articles for enhancing wellness associated with habitable environments
CN108522538A (zh) * 2017-03-01 2018-09-14 浙江源程环保科技有限公司 一种水体消毒剂
US11668481B2 (en) 2017-08-30 2023-06-06 Delos Living Llc Systems, methods and articles for assessing and/or improving health and well-being
US11649977B2 (en) 2018-09-14 2023-05-16 Delos Living Llc Systems and methods for air remediation
US11844163B2 (en) 2019-02-26 2023-12-12 Delos Living Llc Method and apparatus for lighting in an office environment
US11898898B2 (en) 2019-03-25 2024-02-13 Delos Living Llc Systems and methods for acoustic monitoring
US11647752B2 (en) 2020-10-28 2023-05-16 Hubei Institute of Tobacco Science Method for controlling tobacco bacterial wilt and application of NaHS in controlling tobacco bacterial wilt
CN112262855A (zh) * 2020-10-28 2021-01-26 湖北省烟草科学研究院 一种防治烟草青枯病的方法及NaHS在防治烟草青枯病菌中的应用
IT202100022595A1 (it) * 2021-08-31 2023-03-03 Ntc S R L Composto in forma di particelle funzionalizzate con metallo ionico ad alta percentuale, e suo uso come antimicrobico
WO2023031822A1 (fr) * 2021-08-31 2023-03-09 Ntc S.R.L. Composé sous forme de particules fonctionnalisées ayant un métal ionique à fort pourcentage, et son utilisation en tant qu'agent antimicrobien

Similar Documents

Publication Publication Date Title
WO2008135093A1 (fr) Produits comprenant une composition anti-microbienne à base de nanoparticules de dioxyde de titane
Strayer-Scherer et al. Advanced copper composites against copper-tolerant Xanthomonas perforans and tomato bacterial spot
Strayer et al. Low concentrations of a silver-based nanocomposite to manage bacterial spot of tomato in the greenhouse
Young et al. Multimodal generally recognized as safe ZnO/nanocopper composite: A novel antimicrobial material for the management of citrus phytopathogens
EP2234494B1 (fr) Couche de protection pour plantes et arbres, fabrication et utilisation
US9271502B2 (en) Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
US10004234B2 (en) Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
Bhattacharyya et al. One-pot fabrication and characterization of silver nanoparticles using Solanum lycopersicum: an eco-friendly and potent control tool against rose aphid, Macrosiphum rosae
US9718739B2 (en) Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
Kora Copper-based nanopesticides
US9487453B2 (en) Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
US20170071212A1 (en) Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
Mulwandari et al. Direct synthesis of lemongrass (Cymbopogon citratus L.) essential oil-silver nanoparticles (EO-AgNPs) as biopesticides and application for lichen inhibition on stones
Smith et al. Multifunctional surface, subsurface, and systemic therapeutic (MS3T) formulation for the control of citrus canker
US20160137564A1 (en) Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
Kashyap et al. Tiny but mighty: metal nanoparticles as effective antimicrobial agents for plant pathogen control
Madhusudhanamurthy et al. Organic-Inorganic hybrids of nano silica and certain botanical compounds for their improved bioactivity against agricultural pests
Rajkuberan et al. Multifunctional copper-based nanocomposites in agroecosystem applications
AU2015264306B2 (en) Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
KR100623179B1 (ko) 개봉이 용이한 항균 과수보호봉지
KR101463656B1 (ko) 식물탄저병 방제용 은나노 조성물
US20220079147A1 (en) Compositions and methods for systemic delivery of cagos in vascular plants
EP4120832A1 (fr) Plantes protégées et leurs procédés d'obtention
Liu Development of akaganéite (β-FeOOH, Cl) nanoparticles (Ak NPs), modified polyvinyl alcohol-Ak composites, and chitosan-Lemon Myrtle essential oil conjugates for green antioxidant and antimicrobial food packaging
US20230000077A1 (en) Phytosanitary agent and its particular use in the treatment of plants infected by xylella fastidiosa

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07728905

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07728905

Country of ref document: EP

Kind code of ref document: A1