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WO2008043396A1 - Material, item and products comprising a composition having anti-microbial properties - Google Patents

Material, item and products comprising a composition having anti-microbial properties Download PDF

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Publication number
WO2008043396A1
WO2008043396A1 PCT/EP2006/067361 EP2006067361W WO2008043396A1 WO 2008043396 A1 WO2008043396 A1 WO 2008043396A1 EP 2006067361 W EP2006067361 W EP 2006067361W WO 2008043396 A1 WO2008043396 A1 WO 2008043396A1
Authority
WO
WIPO (PCT)
Prior art keywords
product
composition
product according
group
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2006/067361
Other languages
French (fr)
Inventor
Carlo Alberto Bignozzi
Valeria Dissette
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NM Tech Nanomaterials and Microdevices Technology Ltd
Original Assignee
NM Tech Nanomaterials and Microdevices 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
Priority to EP11196096.9A priority Critical patent/EP2452561B1/en
Priority to US12/445,307 priority patent/US8389022B2/en
Priority to PL11196094T priority patent/PL2452560T3/en
Priority to ES11196094.4T priority patent/ES2487665T3/en
Priority to EP11196093.6A priority patent/EP2452559B1/en
Priority to PCT/EP2006/067361 priority patent/WO2008043396A1/en
Priority to EP06807226.3A priority patent/EP2079302B1/en
Priority to EP11196094.4A priority patent/EP2452560B1/en
Priority to HK10101324.3A priority patent/HK1137621B/en
Priority to PL06807226T priority patent/PL2079302T3/en
Priority to EP11196092.8A priority patent/EP2452558B1/en
Priority to JP2009531723A priority patent/JP2010505887A/en
Application filed by NM Tech Nanomaterials and Microdevices Technology Ltd filed Critical NM Tech Nanomaterials and Microdevices Technology Ltd
Priority to ES06807226.3T priority patent/ES2486867T3/en
Priority to CN2006800564262A priority patent/CN101588715B/en
Publication of WO2008043396A1 publication Critical patent/WO2008043396A1/en
Anticipated expiration legal-status Critical
Priority to HK12110678.4A priority patent/HK1170119B/en
Priority to HK12110677.5A priority patent/HK1170118B/en
Priority to HK12110680.0A priority patent/HK1170120B/en
Ceased legal-status Critical Current

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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/28—Rubbing or scrubbing compositions; Peeling or abrasive compositions; Containing exfoliants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • Material, item and products comprising a composition having anti-microbial 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 nanomaterials, nanomaterial products, material and items comprising a nanomaterial composition having antibacterial, antimicrobial, antiviral, antimycotic, germicide, photo-remediating properties .
  • the invention relates to a product for topical use having antibacterial, antimicrobial, antiviral, antimycotic, germicide properties.
  • the contagion could be very dangerous, for example for newborn babies, or old persons, or patients in hospitals.
  • bacteria proliferations are, on the one hand very common, and on the other hand it is very important to limit and avoid such proliferations.
  • In agriculture it is often necessary to treat plants, or fruit trees, or vegetables, or also flowers, with specific products to eliminate bacteria, or fungi or other microorganisms, and to avoid a proliferation thereof that would adversely affect the quality of the vegetables or of the fruit, or would compromise the entire harvest of the farmer .
  • Such scars are unsightly, also the scars are mainly on the skin of the face and therefore may not be hidden with clothes or scarves, and have to be thermally treated to be eliminated. Therefore such scares cause many problems mainly for relations with other persons. Similar problems may arise for a person affected by Herpes virus .
  • Such virus creates painful and unsightly vesicles, particularly in the skin of a face of a person. Such vesicles may create many problems for the relationships of a person affected thereby.
  • the vesicles are caused by a virus, it is very important to avoid any contagion by the virus of other zones of the skin of an affected person previously free of vesicles, and also to avoid any contagion of other persons.
  • ulcers, excoriations, etc. may be infected by external microbes and the recovery becomes slower and very strong medicine have to be taken in order to try treating the infection .
  • a cicatrizing product is often required that has a good cutaneous compatibility and is also efficacious in cicatrizing the skin and avoiding any external contagion to the wound to be cicatrized.
  • many persons suffer because they smell of sweat and/or because have body odour, and have many problems in relationships with other persons.
  • An object of the invention is to improve known coatings, such as for example, tiles, panels, carpeting, rugs, and linoleum coatings, known furniture, known materials.
  • Another object is to provide coatings, such as for example, tiles, panels, carpeting, rugs, linoleum coatings, furniture, materials, having antibacterial, antimycotic, antiviral, anti-pollution, self-cleaning properties. Still another object is to improve known cleansing products. Another object is to provide cleansing products having antibacterial, antimycotic, antiviral properties. Still another object is to improve known painting products. A further object is to provide a painting product having antibacterial, antimycotic, antiviral, anti-pollution, self- cleaning properties.
  • a further object is to improve the properties of known items. Still further object is to provide items having antibacterial, antimycotic, antiviral, anti-pollution, self- cleaning properties.
  • Still further object is to provide filter means, in particular to be used in air-conditioning systems, having antibacterial, antimycotic, antiviral, anti-pollution, self- cleaning properties. Another object is to provide surgical instruments having antibacterial, antimycotic, antiviral properties. Still another object is to provide sanitary napkin means and/or linen means having antibacterial, antimycotic, antiviral properties. A further object is to improve known topical-treatment means, such as cream means, gel means, or powder means for topical use . Another object is to provide topical-treatment means having antibacterial, antimycotic, antiviral properties.
  • Still another object is to provide topical-treatment means for treating skin ulcers, and in particular bedsores, or decubitus ulcers.
  • a further object is to provide topical-treatment means for treating cutaneous irritations, and/or inflammations, and/or abrasions, and/or excoriations, and/or burns.
  • a further object is to provide topical cicatrizing means for cicatrizing the skin of a user thereof. Another object is to provide a lenitive topical-treatment means for relieving topical affections.
  • a further object is to provide deodorizing means for topical use for deodorizing the skin of a user.
  • a coating product comprising a composition having the general formula AO x - (L-Me n+ ) x .
  • a method for obtaining coating means comprising adding a coating product with a composition having the general formula AO x - (L-Me n+ ) x .
  • 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 the number of (L-Me n+ ) groups bound to the metal oxide AO x , and 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.
  • such a coating product maintains antibacterial, antiviral, antimycotic properties over time, avoiding any subsequent bacteria proliferation on the treated surface.
  • a surface can be obtained, for example a wall of a building, of a room, that maintains over time the antibacterial, antiviral, antimycotic properties. The need for subsequent treatments for reclaiming antibacterial properties is therefore avoided.
  • Such coating product maintains also self-cleaning properties; therefore, it is possible to obtain a self-cleaning surface, avoiding the necessity of subsequent treatments for removing pollution therefrom. Further, in case of necessity, it is possible to restore the properties of the coating product, in case for example of depletion of the metal ion(s), for example by wetting such a coating product with an alcoholic solution containing the same metal ion(s) present into the composition having the general formula AO x - (L-Me n+ ) x .
  • the very limited particle size of the composition having the general formula AO x - (L-Me n+ ) ⁇ allow finely disperse such composition into the structure of the coating product, and therefore a coating product having homogeneous properties can be obtained. Moreover, with such a coating product can be obtained homogeneous film that would homogeneously cover a surface on which such coating product is applied.
  • metal or metalloid oxide AO x adhere to any different suitable substrate, and in case, by further adding a particular additive to the coating product, it is possible to obtain a coating product that can be suitably applied to several different substrates, such as for example wood, plastic, glass, metals, ceramics, cement, and internal and external building surfaces. Further, such coating product has antibacterial, anti- pollution activity also in absence of solar light, or of any other light source, and can therefore be applied to any desired substrate assuring hygienic conditions thereof. In case, before applying such a coating product to the desired surface, a primer can be applied on the surface so as to enhance the adhesion of the coating product and to protect the surface.
  • the coating product can comprise a painting product .
  • pigment means, and/or binder means, and/or filler means, and/or diluting means, and/or additive means may be mixed to the painting product for obtaining a painting product having the desired features, such as for example, density, colour, consistency, etc., and for obtaining a paint substrate having the desired propertied such as for thickness, colour, brightness, or opacity, etc..
  • composition AO x - (L-Me n+ ) x can be used for obtaining suspensions either in aqueous or in other solvents, for example polar solvents, therefore different kind of a coating products suitable for being applied to different kind of surfaces can be obtained.
  • such a coating product can be used for coating plastics, ceramics, synthetic materials, natural rubber, synthetic rubber, wood, natural stone, marble, metal, aluminium, iron, glass, cement, linoleum, textiles, carpeting, rugs, etc., provided with antibacterial, antimicrobial, anti-pollution, properties. It is also possible to obtain an anti-pollution coating product allowing organic and inorganic pollution to be removed form a surface on which such coating product is applied, and/or from a medium contacting such coating product, and avoiding any pollution, or dirty deposition thereon.
  • the solvent of the coating product it is also possible to obtain transparent coating product that could be applied on to a desired surface without altering the aesthetical appearance thereof. Therefore such a coating product could be applied for example, on statues, aesthetical creations, external surface of building that are located outside, and, therefore subjected to air pollution. Further, by adding a desired pigment it is possible to obtain a coloured coating product.
  • suspensions of the composition AO x - (L-Me n+ ) x are stable over time, and therefore coating products that are stable over time can be obtained, avoiding the need to mix the components of the coating product only just before applying such coating product.
  • a stain can be obtained, that can be subsequently in turn used for obtaining a painting product. It is also possible to obtain material provided with a coating product conferring to said material antibacterial, antiviral, antimycotic, self-cleaning, photocatalytic, anti- mildew properties.
  • a product comprising a base material and a composition having the general formula AO x - (L-Me n+ ) x .
  • a method for producing a material wherein coating said material with a coating product comprising a composition having the general formula AO x - (L-Me n+ ) x it is provided for.
  • a method for producing a product comprising mixing with a base material of said product a composition having the general formula AO x - (L-Me n+ ) x .
  • a composition having the general formula AO x - (L-Me n+ ) ⁇ is suitable for being applied to, or mixed with, in case diluted with suitable solvents, any desired materials, therefore many different materials and products with antibacterial properties can be obtained.
  • such a composition can be used for obtaining plastics, ceramics, synthetic materials, natural rubber, synthetic rubber, wood, natural stone, marble, metal, aluminium, iron, glass, cement, linoleum, textiles. Furthermore, materials with very homogeneous properties can be obtained. Such a composition may be mixed to a base material in flowable state obtaining a product having the aforementioned properties .
  • Such a composition can further be mixed with a desired base material during the preparation process of a product, for example can be added to melt plastics, or glass intimately mixing with the structure of the plastics.
  • plastics, or glass material having a very homogeneous structure in which structure the composition having the general formula AO x - (L-Me n+ ) x is very homogeneously mixed, and therefore antibacterial properties are homogeneously present in such materials.
  • Materials and products obtained have no bacteria proliferation centre and have very high hygienic conditions. Such materials can be used for making object, items, coating means provided with antibacterial properties.
  • a cleansing product comprising a composition having the general formula AO x - (L-Me n+ ) x .
  • a method for preparing cleansing means comprising adding a cleansing product with a composition having the general formula AO x -(L-Me ⁇ ) 1 .
  • a cleansing product having antibacterial, antimicrobial, antiviral, antimycotic, anti-pollution properties that can be used for cleaning a desired surface, reclaiming hygienic properties thereof.
  • Such a cleansing product can be used for example for cleaning floors, or walls in hospitals, schools or other public facilities, for cleaning bathrooms, public baths, showers, so avoiding bacteria proliferation.
  • a cleansing product efficacious against many microorganisms such as for example: HSV-I (Herpes Simplex Virus-1) , Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherica CoIi, Salmonella enteridis Dl, Listeria monocytogenes, Candida albicans, Aspergillus niger, may be obtained.
  • HSV-I Herpes Simplex Virus-1
  • Poliovirus Poliovirus
  • Aviaria virus Legionella pneumophila
  • Pseudomonas aeruginosa Staphilococcus aureus
  • Enterococcus faecalis Enterococcus faecalis
  • Escherica CoIi Salmonella enteridis Dl
  • Listeria monocytogenes Candida albicans
  • Candida albicans
  • said cleansing product comprises surfactant means for improving the removal of dirty, and/or abrasive means for improving the removal of dirty, and/or pH modifying means for improve the efficacy of the cleansing, and/or water softener means for counteracting the hardness of the water, oxidant means for bleaching, non-surfactant means for keeping dirty in suspension, enzyme for digesting proteins, fats, or carbohydrates in dirty, or for modifying fabric fel, foaming modifying means, optical brightener, and/or colour means, and/or perfume means, and/or essence means for improving the removal of dirty, or the efficacy and the performances of the cleansing product.
  • the cleansing product further comprises sodium laureth sulfate, and/or glycol distearate, and/or natural oil means, and/or coconut oil, and/or inseed oil, and/or tocopherol, and/or pantothetic acid.
  • a sterilising product comprising a composition having the general formula AO x - (L-Me n+ ) x .
  • a method for preparing a sterilising product comprising adding a composition having the general formula AO x - (L-Me n+ ) ⁇ there is provided for.
  • a method for sterilising object comprising bringing said object into contact with a sterilising product comprising a composition having the general formula AO x - (L-Me n+ ) x .
  • a method for sterilising surgical instruments comprising bringing said surgical instruments into contact with a sterilising product comprising a composition having the general formula AO x - (L-Me n+ ) x .
  • a fourteenth aspect of the invention there is provided a method for obtaining surgical instruments comprising at least partly coating said surgical instruments with a coating product with a composition having the general formula AO x - (L-Me ⁇ ) 1 .
  • a biocide product comprising a composition having the general formula AO x - (L-Me n+ ) x .
  • a method for preparing biocide means comprises adding a biocide product with a composition having the general formula
  • a biocide product comprising a composition having the general formula AO x - (L-Me n+ ) lr there is provided for. Owing to these aspects of the invention, it is possible to obtain a biocide product that is efficacious for removing several different organisms, such as bacteria, fungi, sponges, and mildews.
  • biocide product that could be spread on the desired surface either by spraying, or be applied to the desired surface.
  • biocide product that is very efficacious for removing bacteria as, for example
  • Pseudomonas Erwinia amilovora , Xanthomonas campestris, fungi, from plants, flowers, trees.
  • a prosthesis product comprising a composition having the general formula AO x - (L-Me n+ ) ⁇ .
  • a method for preparing a prosthesis means comprising at least partly coating said prosthesis means with a coating product comprising a composition having the general formula AO x -(L-Me ⁇ ) 1 .
  • a method for preparing prosthesis means comprising mixing prosthesis material with a product comprising a composition having the general formula AO x - (L-Me n+ ) x .
  • filter means provided with a coating product comprising a composition having the general formula AO x - (L- Me n+ K.
  • a method for preparing filter means comprising at least partly coating said filter means with a coating product comprising a composition having the general formula AO x - (L- Me n+ K.
  • filtering systems such as for example air- conditioning systems that would do not contribute to spreading infections, but remove any bacteria or other microorganisms, or pollution from the air circulating therein .
  • Air-circulating systems improving the quality of the air in a room or in a building can thus be obtained.
  • a method for preparing sanitary napkin means comprising mixing a product having the general formula AO x - (L-Me 11 ) ! to absorbent material means of said sanitary napkin means .
  • a method for obtaining sanitary napkin means comprising applying a product having the general formula AO x -
  • a sanitary napkin product comprising a composition having the general formula AO x - (L-Me n+ ) x .
  • a method for sanitizing sanitary napkin means comprising bringing said sanitary napkin means into contact with a product having the general formula AO x - (L-Me n+ ) ⁇ .
  • a method for sanitizing linen means comprising bringing said linen means into contact with a product having the general formula AO x - (L-Me n+ ) x .
  • a composition with the general formula AO x - (L-Me n+ ) x for obtaining a topical-treatment product for treating acne diseases .
  • a composition having the general formula AO x - (L-Me n+ ) ! for a obtaining topical-treatment product for treating herpes diseases.
  • a composition having the general formula AO x - (L-Me n+ ) ! for a obtaining topical-treatment product for treating skin ulcers, and in particular decubitus ulcers.
  • composition a having the general formula AO x - (L-Me n+ ) x for obtaining a topical-treatment product for treating skin irritations, and/or skin inflammations, and/or skin abrasions, and/or skin excoriations .
  • composition having the general formula AO x - (L-Me n+ ) ! for obtaining a lenitive topical-treatment product .
  • a composition having the general formula AO x - (L-Me n+ ) x for obtaining a cicatrizing topical- treatment product for cicatrizing the skin of a user of said cicatrizing product.
  • a composition having the general formula AO x - (L-Me n+ ) ! for obtaining a burn topical-treatment product for treating burns on the skin of a user of said topical- treatment product.
  • topical-treatment products efficacious against many different diseases may be obtained, moreover, topical-treatment products having antiviral, antibacterial, antimicrobial, antimycotic may be obtained.
  • topical-treatment products having antiviral, antibacterial, antimicrobial, antimycotic may be obtained.
  • HSV-I Herpes Simplex Virus-1
  • Poliovirus Poliovirus
  • Aviaria virus Legionella pneumophila
  • Pseudomonas aeruginosa Staphilococcus aureus
  • Enterococcus faecalis Escherica CoIi
  • Salmonella enteridis Dl Listeria monocytogenes, Candida albicans, Aspergillus niger.
  • the composition having the general formula AO x - (L- Me 11 ⁇ 1 further comprises a quaternary ammonium salts for enhancing the antiviral, antibacterial, antimicrobial, antimycotic properties of the topical-treatment means.
  • a method for obtaining a topical-treatment product for treating acne diseases comprising adding a composition having the general formula AO x - (L-Me n+ ) x .
  • a method for obtaining a topical-treatment product for treating herpes diseases comprising adding a composition having the general formula AO x - (L-Me n+ ) x .
  • a method for obtaining a topical-treatment product for treating skin ulcers, and in particular decubitus ulcers comprising adding a composition having the general formula AO x - (L-Me 11 ⁇ 1 .
  • topical-treatment products efficacious against many different diseases may be obtained, moreover topical-treatment products having antiviral, antibacterial, antimicrobial, antimycotic properties may be obtained.
  • HSV-I Herpes Simplex Virus-1
  • Adenovirus Poliovirus
  • Aviaria virus Legionella pneumophila
  • Pseudomonas aeruginosa Staphilococcus aureus
  • Enterococcus faecalis Enterococcus faecalis
  • composition having the general formula AO x - (L-Me n+ ) x may be added to any known topical-treatment products to thus obtain topical-treatment products for example in form of cream, or gel, or powder, means having antibacterial, antimicotic, virucidal, antimicrobial properties.
  • topical-treatment products for example in form of cream, or gel, or powder
  • means having antibacterial, antimicotic, virucidal, antimicrobial properties for example such composition may be added to a common daily, or night cream, or to a moisturizing cream, thus conferring the aforementioned properties thereupon.
  • topical-treatment products having antiviral, antibacterial, antimicrobial, antimycotic properties, together with other curative properties. Therefore very efficacious topical-treatment products may be obtained.
  • the antiviral, antibacterial, antimicrobial, antimycotic properties allow the curative properties of the topical-treatment products to be enhanced since any microbial proliferation growth is avoided, and any spread of the contagion to different areas of the skin is also avoided, and also any external contagion is also avoided.
  • the topical-treatment product comprises cream means, gel means, and/or powder means.
  • the elements in the composition having the general formula AO x - (L-Me n+ ) ⁇ may be obtained a product compatible and thus mixable with any physical form of the cream means, for example emulsions, gels, suspensions, foams, microbeadlets, microspheres, granules, microgranules, multiple emulsions, e.g. water-in- oil-in-water emulsions.
  • very homogeneous topical-treatment products may be further obtained.
  • a deodorizing product comprising a composition having the general formula AO x - (L-Me n+ ) x .
  • said deodorizing product is in powder form. In a further version said deodorizing product is in spray, and/or cream form, and/or gel form, and/or aerosol form.
  • composition having the general formula AO x - (L-Me n+ ) lr deodorizing product having very homogeneous properties may be obtained.
  • a composition having the general formula AO x - (L-Me n+ ) ! for obtaining a deodorizing product. Owing to the properties of the composition having the general formula AO x - (L-Me n+ ) ⁇ it is possible to obtain very efficacious deodorizing products, and also deodorizing products having antibacterial, antimicrobial, antimycotic, virucidal properties.
  • AO x - (L-Me n+ ) x By suitably choosing the compounds in the composition having the general formula AO x - (L-Me n+ ) x it is possible to obtain deodorizing products having a great cutaneous compatibility, a great efficacy in deodorizing the skin of a user thereof, and also a great efficacy in avoiding any microbial growth.
  • AO x - (L-Me n+ ) lr AO x may be for example titanium dioxide (TiO 2 ) , zinc oxide (ZnO) , stannic oxide
  • Me n+ may be for example a transition metal ion, for example Ag + Cu ++ .
  • 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 (- PO3H2) (or phosphonate) , or boronic (-B(OH) 2 ) (or boronate) , dipyridyl group, terpyridyl group.
  • the second functional may be chosen in a group comprising: Cl “ , Br “ , I “ , S, 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. If more than one dipyridylic group or terpyridylic group is present, one of these groups may be unsubstituted.
  • the bifunctional ligands L of organic type 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 (-B(OH) 2 ), phosphonic (-POsH 2 ), mercaptan (-SH), and hydroxyl (- OH) ; - C6 to C18 aryls, preferably selected from: phenyl, naphthyl, biphenyl, and possibly substituted with one or more substituents selected preferably between: carboxyl
  • 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 first functional group and the second functional group of ligand L may also be both coordinated at a metallic centre (M) of the ligand L.
  • the metallic element of the ligand L may have a coordination of the octahedral type or different kind of coordination corresponding to tetrahedral geometry, rectangular planar, square planar geometry, bipyramidal trigonal geometry, or pyramidal geometry with a square or rectangular base, and any of the metals which are in the first, second, or third row of transition metals in the periodic table of the elements and which can give rise to stable bifunctional molecules of the type described may be used.
  • the transition metal coordinated by the ligand L is selected from: Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Re, Os, Ir, and Pt.
  • the ligand L may have a negative charge, and may form salts with cations, preferably organic cations such as tetraalkylammonium cations.
  • cations preferably organic cations such as tetraalkylammonium cations.
  • ion Me n+ is chosen between Ag + and/or Cu ++ having antibacterial, antimycotic, antiviral, activity.
  • metal oxide AO x comprises TiC>2, preferably with titanium in Anatase form, therefore an anti- pollution, photocatalytic composition can be obtained.
  • Such composition has particle size less than 30nm, more preferably less than 15nm.
  • quaternary ammonium salts may be added to the composition having the general formula AO x - (L-Me n+ ) ⁇ so enhancing the antiviral, antibacterial, antimicrobial, antimycotic properties of the composition.
  • Quaternary ammonium salts are positively charged polyatomic ions of the structure NR 4 + X " with Rl, R2, R3, R4 being alkyl groups, and X ⁇ a suitable anion, for example chloride anion Cl " . Any or all of the R groups may be the same or different alkyl groups. Many of quaternary ammonium salts are widely used, for example chloride ammonium salts.
  • Quaternary ammonium salts are used for example as disinfectants, surfactants, fabric softeners, antistatic agents (e.g. in shampoo). Adding suitable quaternary ammonium salts to the composition having the general formula AO x - (L-Me n+ ) ⁇ it is possible to improve the stability of suspensions, or emulsions or solutions of the composition having the general formula AO x -
  • quaternary ammonium salts it is also possible to enhance the cleaning properties of a detergent product.
  • tetraalkylammonium salt, and/or alkylammonium salts, and/or benzalkonium chloride may be added to the composition having the general formula AO x - (L-Me n+ ) x .
  • AO x - (L-Me n+ ) x may be added to the composition having the general formula AO x - (L-Me n+ ) x .
  • AO x - (L-Me n+ ) x is efficacious against several different microorganisms such as for example bacteria, fungi, sponge, mildews, and also for removing organic and inorganic pollutions.
  • Virus-1) Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus,
  • a coating product, painting means, a material, a cleansing product, a sterilising product, topical-treatment means, deodorizing means, objects, items effective in removing such microorganisms and in avoiding further proliferation thereof can be obtained.
  • Figure 1 schematically illustrates the structure of a composition having the general formula AO x - (L-Me n+ ) ⁇ ;
  • Figure 2 a schematic representation of a particular composition having the general formula AO x - (L-Me n+ ) ⁇ ;
  • AO x is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (0) bonded to the metal (A) atom
  • 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+ is a metal ion, having antibacterial, antiviral, antimycotic activity, for example Ag + , Cu ++ .
  • L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AO x ) and the metal ion (Me n+ ) , and i is the number of (L-Me n+ ) groups bound to the metal oxide AO x ; 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.
  • Bifunctional molecules L may be organic or organometallic molecule, as in the example in Figure 2, such as complexes of the transition metals.
  • Ligand L may be provided with different suitable functional groups, first functional group such as carboxyl (-COOH) (or carboxylate) , phosphonic (-PO3H2) (or phosphonate) , or boronic (-B(OH) 2 ) (or boronate) , dipyridyl group, terpyridyl group, bonding to the AO x oxide, and second functional group such as Cl “ , Br “ , I “ , CNS “ , NH 2 , CN “ and NCS " , bonding the Me n+ ions.
  • first functional group such as carboxyl (-COOH) (or carboxylate) , phosphonic (-PO3H2) (or phosphonate) , or boronic (-B(OH) 2 ) (or boronate)
  • dipyridyl group such as a phosphonic (-PO3H2) (or phosphonate)
  • boronic (-B(OH) 2 ) or boronate
  • dipyridylic or terpyridylic group is substituted with carboxyl group, more preferably in para position with respect to the pyridine nitrogen.
  • one of these groups may be unsubstituted.
  • First functional group and second functional group of ligand L may also be both coordinated at a metallic center (M) of the ligand L, as in the case in Figure 2.
  • M metallic center
  • the transition metal coordinated by the ligand L is selected from: Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Re, Os, Ir, and Pt.
  • the ligand L may have a negative charge, and may form salts with cations, preferably organic cations, more preferably quaternary ammonium cations, such as tetraalkylammonium cations .
  • composition may be mixed with cationic surfactants, such as alkylammonium salts, benzalkonium chloride, that would also enhance the bactericidal activity of the composition
  • cationic surfactants such as alkylammonium salts, benzalkonium chloride
  • TiO 2 , ion Me + , is Ag + and ligand L is a metallorganic molecule having the general formula Ru (H 2 dcb) 2 (NCS) 2 , in which
  • composition AO x - (L-Me n+ ) x nanoparticles are obtained that can be added to a material and intimately mixed to it, obtaining a material, for example a plastic with homogeneous properties. For the same reason very homogeneous emulsions, or suspensions, or solutions in many different solvents may be obtained with the composition AO x - (L-Me n+ ) x .
  • Such composition can be spread, or applied to a surface allowing a very homogeneous coverage and/or coating of the surface to be obtained.
  • compositions having the general formula AO x - (L-Me n+ ) x have particle size less than 40nm, preferably mess than 30nm, more preferably less than 15nm. Therefore very thin and homogenous films homogeneously covering a surface can be obtained.
  • Composition having the general formula AO x - (L-Me n+ ) ⁇ may be used for obtaining suspensions both transparent and milky, both in aqueous and polar solvents, both in inorganic and organic solvents, such suspension being stable over time.
  • a metal or metalloid oxide AO x is mixed with a Ligand L, and with a solution into which ion Me n+ are dissolved.
  • Oxides AO x are usually available as suspension, for example colloidal suspensions, or also in powder form.
  • Colloidal suspension based, for example, on colloidal silica, and/or stannic dioxide are commercially available.
  • Suspension based on titanium dioxide and/or zirconium dioxide may be also prepared, for example as explained thereafter.
  • the afore mentioned suspension may be transparent or opaque, or milky and would affect the colour properties of the final suspension prepared.
  • the suspension of the metal or metalloid oxide AO x are properly mixed with a suitable Ligand L so that a certain number of molecules of the ligand may be absorbed on the surface of a molecule of oxide AO x , as can be seen from the Figure 1, and explained in the following examples.
  • the number of molecules L absorbed to a molecule of the oxide AO x depends on the particular oxide AO x used.
  • the absorption of the ligand L on the molecule of the oxide AO x requires about 12-36 hours, whereas the absorption of the metal ions Me n+ is substantially an instantaneous reaction. Thereafter stable suspensions are obtained in which the ligand L is bound both to the oxide AO x and to the metal ions Me n+ , such suspensions may be used for obtaining many different products, for example the products cited above and in the uses above specified. In some other cases oxide AO x in powder form may be added to a solution containing the ligand L and therefore an alcoholic solution of metal ions Me n+ may be added.
  • cationic surfactants may be absorbed on to oxide AO x and therefore a ligand L, preferably in suspension and/or in solution, and an metal ions Me n+ , preferably in alcoholic solution, may be added and mixed so that the absorption reactions may take place.
  • cationic surfactants may enhance the absorption of the ligand L to the oxide AO x and also the absorption of the metal ions Me n+ on the ligand L. Cationic surfactants may also improve the solubility of the components into the suspensions, improving the stability thereof, and also enhance the antibacterial, antimycotic, antimicrobial properties of the suspensions obtained.
  • composition may be added to any desired known paint thus obtaining a paint having anti-bacterial, antimicrobial, antimycotic, self-cleaning, anti-polluting properties.
  • composition may be added during a desired stage of a process for producing paint.
  • the particular solvents used in the preparation of the suspension of the composition, and or the form of the composition may be chosen in view of a compatibility with the ingredients of the particular paint that it is desired to obtain .
  • composition having the general formula AO x - (L-Me n+ ) ⁇ may be added to a known cleansing product so obtaining a cleansing product having anti-bacterial, antimicrobial, antimycotic, self-cleaning, anti-polluting properties.
  • the composition having the general formula AO x - (L- Me n+ )i may be added to any desired stage of the process for producing a cleansing product to the ingredients of the cleansing product.
  • the form of the composition having the general formula AO x - (L-Me n+ ) ⁇ and/or the particular solvent (s) used for preparing a suspension thereof a wide range of cleansing products may be obtained.
  • composition having the general formula AO x - (L-Me n+ ) ! has been obtained in any desired form, such as suspension, emulsion, solution
  • such composition may be added to the ingredients for preparing topical-treatment products, for example, a cream, a night cream, a lenitive cream or gel, a moisturizing cream or gel, obtaining a topical-treatment product having curative properties.
  • Such a composition may also be added to the ingredients for preparing curative topical-treatment products, for example to a burn cream, enhancing the curative properties thereof and conferring to the curative topical-treatment product antimicrobial, antibacterial, antimycotic, antiviral properties .
  • Example 1 Transparent suspensions based on TiO 2 Into a beaker there were charged 300 mL distilled H 2 O and 2.1 mL of a strong acid, e.g. concentrated HNO3 (65% w/w) . Over a period of 10 min, 50 mL titanium isopropoxide (supplied by Fluka) was added under stirring, by means of a dropping funnel . A white milky precipitate of TiO 2 was formed.
  • the mixture was then heated at 80 °C for 8 to 12 hours, taking care to maintain the stirring and the temperature constant . During the heating, the precipitate redissolves, and the mixture took on an opalescent appearance.
  • the colloidal suspension was concentrated to a final volume of 100 to 200 mL, corresponding to a TiO 2 concentration of 150-75 g/L.
  • the nanoparticles of titanium dioxide obtained at the end of the process had a diameter in the range 6 to 15 nm.
  • the suspension concentrated to 100 mL was then diluted by addition of distilled water and ethanol, to give a final transparent solution (pH ⁇ 2) that has a concentration of TiO 2 of 1.5% and a percentage of alcohol comprised between about 10% to about 50%, preferably of about 25%.
  • Example 2 Transparent suspensions based on ZrO 2
  • zirconium tetraisopropoxide 70% in isopropanol was added under stirring, by means of a dropping funnel.
  • a white milky precipitation of ZrC>2 was seen to form almost immediately.
  • the mixture was then heated at 90 0 C for 8 to 12 hours, taking care to maintain the stirring and to maintain constant temperature.
  • Neutral aqueous opaque suspensions based on titanium dioxide can be obtained by adding titanium dioxide P25 to aqueous solutions of "Triton X 100" (supplied by Fluka) .
  • Neutral aqueous opalescent suspensions based on titanium dioxide may also be prepared from peroxytitanic acid by a modification of a procedure reported in the literature
  • This precipitate is white and has the consistency of a gel.
  • the precipitate is collected on a filter of porosity G3, and is washed with 750-1000 mL distilled water (until complete elimination of the chloride is achieved, as can be demonstrated by treating the liquid filtrate with AgNOs) •
  • the precipitate comprised of titanic acid, Ti(OH) 4 is collected and is suspended in 200 mL distilled water having conductivity less than 1.5 mS and having pH comprised in the interval 5-7; to this there is slowly added over a period of 20-30 minutes 92 mL of 30% H 2 O 2 .
  • the resulting suspension of nanoparticles has a pH close to neutral, and an opaque appearance, and is stable over time.
  • Suspensions obtained according to any one of the examples 1 to 3 or suspensions obtained in any other suitable methods and containing at least metal or metalloid oxide having formula AO x , or in any case metal or metalloid oxide having formula AO x in any other suitable form, for example in powder form, are made to react with a suitable bifunctional ligand (L) so that the ligand L is adsorbed on to the particles of the oxide AO x .
  • the number of molecules of ligand L absorbed on each molecule of oxide AO x depends on the features of the ligand L and of the oxide AO x . Thereafter an aqueous or alcoholic solution containing metal ions Me n+ , for example Ag + or Cu 2+ ions, is added so that the metal ions Me n+ are absorbed on the molecule of the Ligand L, obtaining the structure shown in Figure 1. Therefore a suspension, or a solution, containing a composition having the general formula AO x - (L-Me n+ ) ⁇ is obtained.
  • a cationic surfactant may then be added to the suspension of nanomaterials functionalized with metal ions Me n+ , or may be independently added to or adsorbed onto the oxide AO x
  • Example 4 Adsorption of 4-mercaptophenylboronic acid and Ag+ ions onto "TiO 2 P25" (supplied by Degussa) : To a solution containing 2*10 5 moles of 4- mercaptophenylboronic acid dissolved in 50 mL ethanol there was added 1 g of TiO 2 P25 (supplied by Degussa) . The suspension was stirred 24 hr . 4-mercaptophenylboronic acid has an absorption band at 255 nm, attributable to the ⁇ - ⁇ * transition in the phenolic ring.
  • This electronic absorption band permits the adsorption of the boronic acid onto the surface of the nanomaterial as a function of time to be monitored. It is known that the adsorption occurs by interaction of the boronic function with the surface of the semiconductor.
  • the electronic absorption spectra demonstrate that the quantity of 4-mercaptophenylboronic acid adsorbed on the surface of the "TiO 2 P25" reaches 35% of the initial concentration in 24 hr .
  • the solution was centrifuged 10 min at 4000 rpm, obtaining a clear solution, the solid was washed with 20 mL ethanol, and was then re-suspended with 50 mL ethanol under stirring. To this suspension was added 7.2*10 ⁇ 6 moles of a soluble silver salt, preferably silver lactate or silver acetate.
  • a soluble silver salt preferably silver lactate or silver acetate.
  • the suspension obtained was white in colour, odourless, and stable over time.
  • a suspension containing a composition having the general formula AO x - (L-Me n+ ) x is obtained, in which AO x is TiO 2 , L is 4- mercaptophenylboronic, and Me n+ is Ag + .
  • Example 5 Adsorption of 4-mercaptophenylboronic acid and Ag + ions onto transparent suspensions of TiO 2 obtained according to example 1 , and onto products of the firm NMTech 100 mL of a transparent solution of titanium dioxide prepared according to method (A) and containing 15% TiO 2 was diluted with 100 mL distilled water and with 200 mL of a solution of 0.052 g 4-mercaptophenylboronic acid dissolved in ethanol. The suspension was stirred 24 hr, at the end of which period a spectrophotometric determination revealed that the boronic acid was completely adsorbed on the semiconductor nanoparticles .
  • the concentrated suspension was then diluted with distilled water and ethanol to obtain 1 L of an opalescent suspension (pH ⁇ 2) containing TiC>2 in a concentration of 1.5% and ethanol comprised between about 10% and about 50%, preferably of about 25%.
  • the transparent suspension was found to be indefinitely stable .
  • a suspension containing a composition having the general formula AO x - (L-Me n+ ) ⁇ is obtained, in which AO x is TiO 2 , L is 4- mercaptophenylboronic, and Me n+ is Ag + , and further comprising a quaternary ammonium salt such as benzalkonium chloride.
  • this product will be designated as "Bactercline” , for the sake of brevity.
  • the product "PSO-419 D2" which is similar to the product prepared according to the example 1, and which has a content of TiO 2 of 2% and pH ca. 2, can be converted into an antibacterial and antiviral product using a method analogous to that described above.
  • 50 mL of "PSO-419D2" solution containing 2% TiO 2 is diluted with 2.2 mg 4-mercaptophenylboronic acid (2.05xl0 ⁇ 5 M), and the suspension is stirred 24 hr .
  • To the resulting odourless solution there is added 2.05xl0 ⁇ 5 M silver lactate or silver acetate.
  • Example 6 Adsorption of cationic surfactants onto titanium dioxide Cationic surfactants with antibacterial activity are generally adsorbable onto nanomaterials based on TiO 2 , ZrO 2 , SnO 2 , ZnO and SiO 2 .
  • benzalkonium-type salts such as, for example, benzyl dodecyl dimethyl ammonium chloride, or benzyl hexadecyl dimethyl ammonium chloride, or benzalkonium chloride, causes precipitation of the suspension; whereas in the case of suspensions of nanomaterials with neutral or acid pH the suspension is stable.
  • Indirect tests of the adsorption of benzalkonium chloride on nanomaterials based on TiO 2 at neutral pH employ conductimetric measurements.
  • a 50% (w/v) solution of benzalkonium chloride diluted 1:10 has a conductivity of 4.7 mS . If the volume of this solution is increased by 10 to 15 mL by addition of distilled water, the conductivity is reduced to 3.90 mS. If instead the solution is diluted by adding 5 mL of a neutral suspension of titanium dioxide prepared, according for example to the example 3, from peroxytitanic acid, or the equivalent "AT-03" product at neutral pH, the conductivity measured is 3.60 mS .
  • quaternary ammonium salt may be added or also a mixture of different quaternary ammonium salts, preferably a mixture of salts with the same anion, such as chloride ammonium salts.
  • the 2-2 ' -dipyridyl-4-carboxy-4 ' -carboxylate anion acid (abbreviated "Hdcb") is produced by adding one equivalent of tetrabutylammonium hydroxide (abbreviated TBAOH) to 2,2'- dipyridyl-4, 4 ' dicarboxylic acid (abbreviated H 2 dcb) , which is scarcely soluble and is in solid form.
  • TBAOH tetrabutylammonium hydroxide
  • H 2 dcb 2,2'- dipyridyl-4, 4 ' dicarboxylic acid
  • the ligand in the monocarboxylate form (also called “monoprotonated form"), and as a tetrabutylammonium salt (abbreviated “TBA (Hdcb) "), can thus be solubilized in methanol or ethanol and can be adsorbed on titanium dioxide.
  • TBA tetrabutylammonium salt
  • the ligand TBA(Hdcb) has an absorption band at 294 nm, due to ⁇ - ⁇ * transitions, which allows monitoring of its adsorption onto nanomaterials as a function of time.
  • the ligand is completely adsorbed onto the surface of the nanocrystalline substrate. It is known that the adsorption occurs by interaction of the carboxyl functions with the surface of the semiconductor.
  • the suspension was then centrifuged 10 min at 4000 rpm, and the solid was washed with 50 mL methanol.
  • the nanomaterial obtained, functionalized with the ligand (abbreviated Ti ⁇ 2/TBA (Hdcb) ) , was then finally vacuum-dried at ambient temperature.
  • the two suspensions had different stabilities: the suspension functionalized with copper ions, TiO 2 /TBA[Hdcb] /Cu 2+ , remained stable, while that functionalized with silver ions, TiO 2 /TBA [Hdcb] /Ag + , precipitated over time.
  • Bifunctional organometallic ligands L as previously disclosed can be anchored to neutral suspensions of titanium dioxide prepared, for example according to method of example 3, with the nanomaterials being suspended in alcohol solutions of a concentration of approximately 10 ⁇ 3 -10 ⁇ 4 M of the bifunctional organometallic ligands.
  • the suspension is stirred 12 hr, during which time the organometallic ligand L is completely adsorbed onto the surface of the nanomaterials.
  • the presence of the carboxyl functions enables adsorption of the complex, and homogeneous covering of the nanocrystalline material, for a time of the order of 2-3 hr at 50 0 C, and 12 hr at ambient temperature.
  • a silver salt e.g. silver nitrate, silver lactate, or silver acetate
  • a silver salt e.g. silver nitrate, silver lactate, or silver acetate
  • the testing was conducted by depositing films comprised of the different nanomaterials obtained according to the afore described examples on Petri capsules in contact with a number of colonies of Escherica CoIi greater than 10 4 cfu (colony forming units) .
  • Tests have been conducted for evaluating the bactericidal, antimycotic, virucidal properties of a solution of the product named as "Bactercline” containing a composition having the general formula AO x - (L-Me n+ ) lr in which AO x is TiC>2, L is 4-mercaptophenylboronic, and Me n+ is Ag + , and, in case, further comprising a quaternary ammonium salt such as benzalkonium chloride.
  • Such product may be obtained in any suitable method, for example according to the methods in examples 4, 5, 6.
  • the bactericidal activity of "Bactercline” has been evaluated using the method of dilution and neutralization according to standard method UNI-EN 1276 of April 2000. The following strains were used for the testing: Pseudomonas aeruginosa, Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Salmonella enteridis Dl, Listeria monocytogenes .
  • the "Bactercline" substance tested is bactericidal when used at a concentration of 80% (which turns out to be the maximum testable concentration) , after 5 min of contact in the presence of bovine albumin at a final concentration of 0.3%, according to the method of the standard UNI-EN 1276 of April 2000.
  • “Bactercline” is bactericidal also when used at a concentration of 50%, after 5 min of contact in the presence of bovine albumin at a final concentration of 0.3%, according to the method of the standard UNI-EN 1276 of April 2000, since also at such a concentration a vitality reduction more than 10 5 units is obtained. The bactericidal activity of "Bactercline” is therefore very high.
  • a surface test has also been made for evaluating the bactericidal activity of "Bactercline” according to the standard method UNI-EN 13697 of December 2001.
  • the following strains were used in the tests: Pseudomonas aeruginosa, Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Salmonella enteridis Dl, Listeria monocytogenes, Legionella Pneumophila .
  • the substance being tested was deemed bactericidal against the bacterial strains provided according to the European Standard if for each bacterial strain, at 20 0 C after a contact time of 5 min, a reduction of vitality of at least 10 4 units is obtained.
  • Candida albicans Aspergillus niger.
  • the substance being tested was deemed fungicidal if, for each of the mycotic strains, at 20 0 C after a contact time of 15 min, a reduction of vitality of at least 10 4 units is obtained.
  • the "Bactercline” substance tested is antimycotic against Candida albicans at concentrations of 25%, 50%, and 80%, and against Aspergillus niger at concentrations of 50% and 80% (which turns out to be the maximum concentration testable) , after 15 min of contact in the presence of bovine albumin at a final concentration of 0.3%, according to the method of the standard UNI-EN 1650 of October 2000.
  • the antimycotic activity of "Bactercline” has been evaluated also using the surface test according to standard method UNI-
  • Candida albicans Aspergillus niger.
  • the substance being tested was deemed antimycotic if the logarithm of the antimicrobial activity against the microbial strains provided according to the European Standard was greater than or equal to 3, for 15 minutes of contact at
  • the "Bactercline” substance tested under the stated test conditions is antimycotic against Candida albicans and Aspergillus niger, when used at a concentration of 100%, after 15 min of contact in the presence of bovine albumin at a final concentration of 0.3%, according to the method of the standard UNI-EN 13697 of December 2001. Moreover the virucidal activity of "Bactercline” has been tested.
  • D-MEM modified Dulbecco medium
  • BFS bovine fetal serum
  • a virus concentration (virus titre) of 1x10 cytolytic plaque forming units (Pfu) was used.
  • the number of infectious present in 1 mL of solution may be calculated.
  • a method used provided for determining the number of cytolysis plaques produced by a sufficiently diluted viral suspension and placed in contact with a monolayer of cells.
  • the cells were cultured at 37°C, in the presence of 5% of CO2 in "D-MEM" to which 10% BFS, 1% L-glutamine, and 1% penicillin/streptomycin had been added.
  • the determination of the titre was carried out on plates having 12 wells.
  • the viral stock was diluted to known concentrations in a medium containing 2%
  • the inoculum was drawn off and the infection was blocked by adding a medium containing 1% BFS and 2% human gamma globulin, having the function of inhibiting formation of secondary plaques.
  • the inoculated cultures were incubated at 37 0 C for 2 days, and were monitored until the lysis plaques were visible. At this point, the cells were fixed and were stained with gentian violet. Under an optical microscope, the plaques present in the wells were counted and this count was multiplied by the dilution factor, to obtain the viral titre, in units of Pfu/mL.
  • the "Bactercline" product in the amount of 10 and 50 microliters was contacted with HSV-I having a viral titre of
  • the incubation was carried out in 1 mL of D-MEM medium to which 1% of BFS had been added.
  • the virus was diluted to concentrations of IxIO 3 and IxIO 2 Pfu, and the nearly confluent cultures were inoculated.
  • the cells inoculated with the virus pretreated with "Bactercline” did not have lysis plaques, for either of the pretreatment times and either of the virus dilutions .
  • Example 9 Method for producing a cream for topical use containing the composition having the general formula AO x - (L-
  • composition having the general formula AO x - (L-Me n+ ) ⁇ many different kind of topical-treatment products for topical use may be obtained, since the composition having the general formula AO x - (L-Me n+ ) ⁇ may be suitably mixed with many different substances.
  • a topical-treatment cream to be used for treating acne may be obtained.
  • Table 6 The aforementioned compounds are weighed and dosed.
  • a turboemulsifier is heated up to a temperature of about 65°-
  • Phase "A” The compounds having the value "A” in the fourth column of the above table 1 are introduced into a turboemulsifier and mixed together.
  • the turboemulsifier is heated up to a temperature of about 70°-80°C, so that the compounds in the turboemulsifier melt.
  • Phase "B” A further turboemulsifier is heated up to a temperature of about 75°-80°C. The compounds having the value
  • both the turboemulsifier and the further turboemulsifier are closed, and operated so that the respective compounds in the turboemulsifier and in the further turboemulsifier can be mixed and homogenized.
  • a vacuum pump connected to the turboemulsifier is operated, and the compounds in the further turboemulsifier are poured in the turboemulsifier, i.e. compounds of phase "B" are poured in the compounds of phase "A".
  • the turboemulsifier is operated for a small number of minutes so that the compounds of phase "A" and of phase "B” mix and homogenize together, the real mixing of the mixture can be checked and, if necessary, the turboemulsifier may be newly operated. After the desired mixing of the mixture is obtained, the vacuum pump is operated, and the turboemulsifier is cooled down to a temperature of about 45°C-50°C.
  • the vacuum pump is switched off and the compounds having the value "C" in the fourth column of the above table 6 are introduced into the turboemulsifier .
  • the turboemulsifier and the vacuum pump are both operated so that the compounds can be mixed and homogenized together, and the turboemulsifier is cooled during the homogenizing, down to a temperature of about 20°-30°C. Such a temperature value is maintained for a certain time interval during which the compounds are continuously mixed. After a given time interval has elapsed, the product may be poured out form the turboemulsifier and analyzed. Analysis carried out have demonstrated that the product is very stable over time and can be packed in subsequent packing operations and stocked without any risk of separations of the single compounds of the product.
  • the product obtained is an emulsion containing the composition having the general formula AO x - (L-Me n+ ) x and additives and/or other active principles that can be used for preparing topical-treatment products.
  • Such an emulsion is in creamy state and can be used for treating many diseases, and in particular, acne diseases. Owing to the very limited dimension of the composition having the general formula AO x - (L-Me n+ ) ⁇ and the features thereof, an emulsion having very homogenous features is obtained.
  • composition having the general formula AO x - (L-Me n+ ) ⁇ may for example be used a composition containing titanium dioxide (TiO 2 ) as AO x , silver perchlorate (Ag + ClO 4 " ) as Me n+ and a bifunctional ligand L suitable to bond both the titanium dioxide and the silver perchlorate.
  • 2 g of the composition having the general formula AO x - (L-Me 11"1" ) ! contain 1.998g of TiO 2 , 0.0084g of AgClO 4 , and 0.0062g of 4-mercaptophenyl boronic acid as bifunctional ligand L.
  • a quaternary ammonium salt is also present, i.e. benzalkonium chloride .
  • Similar preparations may also be obtained using as bifunctional ligand L 6-mercaptonicotinic acid, and/or 11- mercaptoundecanoic acid, and/or mercaptosuccinic acid.
  • "Bactercline acne” is a creamy, odourless emulsion, having a white colour, with a density of about 0.995-1.005 g/cm 3 , and a viscosity of about 50,000-60,000 centipoises.
  • the creamy emulsion obtained may be spread on the skin, preferably twice a day, owing to the physical features thereof the cream may be spread very easily, and forms on the skin of a user a protective layer, that is invisible and thus not unsightly, and that disinfects the skin allowing the acne diseases to be treated.
  • the cream forms on the skin of a user a protective layer that has a multiple action: it protects the area of the skin lesions from any external infections, and/or microbial infections, protects such area from any external aggression due, for example, to the wind and/or sun radiation, and also prevents any contagion spreading over different areas of the skin of the user, and also any microbial proliferation over such area.
  • Such a cream may also be usefully used for treating herpes virus topical diseases. By spreading the cream twice a day on the skin affected by herpes, skin lesions due to herpes are healed, and any further contagion in different areas of the skin of the user is prevented.
  • the process for producing the cream is very simple and the phase of adding the composition having the general formula AO x - (L-Me n+ ) ! does not interfere with an usual process for producing a topical-treatment product.
  • Topical-treatment products that can be used for different topical uses and for treating many different diseases may be thus obtained.
  • the composition having the general formula AO x - (L-Me 11 ⁇ 1 may be added to many different kind of topical- treatment products, such as vanishing cream, shaving cream, anti-wrinkle cream, moisturizing cream, protective cream, daily cream, or night cream, giving to the topical-treatment product the antibacterial, antiviral, antimicotic properties.
  • composition having the general formula AO x - (L- Me n+ )i may also be added to topical-treatment products in other forms than cream, such as for example gel, tissues soaked with active principles, wipes, patches, liquid crystals, liquid compositions with two or more distinct layers, dispersions, emulsions, suspensions, foams, microbeadlets, microspheres, granules, microgranules, microemulsions ; nanoemulsions, multiple emulsions, e.g. water-in-oil-in-water, encapsulated compositions.
  • the topical-treatment product produced according to the aforementioned process and containing the compounds of the aforementioned table is efficacious against the following microbes: bacteria: Pseudomonas aeruginosa, Staphylococcus aureus, Staphylococcus epidermidis, Enterococcus faecalis, Escherichia coll, Salmonella enteriditis Dl, Listeria monocytogenes, Legionella Pneumofila ; fungi: Candida albicans, Aspergillus niger; virus: Herpes virus.
  • Tests have been conducted to evaluate the virucidal efficacy of "Bactercline acne" against different viruses and in particular against Poliovirus and Adenovirus . Tests were conducted according to the standard procedure described in "European Standard EN14476, May 2002 (phase 2 ; step 1) edited by the European Standardization Committee to evaluate the virucidal activity of "Bactercline acne”. A certain quota of a viral suspension was added to "Bactercline acne” both in "clean state”, i.e. in a water solution containing 0.3 g/1 of bovine albumin, and in "dirty state", i.e. in a water solution containing 3.0 g/1 of bovine albumin and 0.3 ml of erythrocytes.
  • Adenovirus type 5 ATCC VR5
  • Poliovirus 1 Sabin strain having a titre, evaluated as Logio of ID 50 , respectively of Adenovirus type 5 5-8.15 for
  • a certain quantity of the mixture containing the viral suspension and "Bactercline acne" was removed, diluted using a 1:10 dilution ratio with a Minimal Essential Medium (MEM) and 2% of Fetal Calf Serum (FCS) to block the virucidal activity, and then analyzed for evaluating the virucidal activity.
  • MEM Minimal Essential Medium
  • FCS Fetal Calf Serum
  • the virucidal activity was evaluated calculating the ID 50 i.e. the dilution of the viral suspension that causes cytopathic effects in 50% of the samples, as according to the "Spearman-Karber method".
  • Example 10 Method for producing a topical-treatment product containing the composition having the general formula AO x - (L-
  • composition having the general formula AO x - (L-Me n+ ) x many different kind of topical-treatment products may be obtained, since the composition having the general formula AO x - (L-Me n+ ) ! may be suitably mixed with many different substances .
  • a product to be used for treating ulcers and in particular bedsores, or decubitus ulcers, may be obtained.
  • table 9 the percentage contents of a cream for topical use for treating ulcers are indicated.
  • the aforementioned compounds are weighed and dosed.
  • a turboemulsifier is heated up to a temperature of about 65°-
  • Phase "A” The compounds having the value "A” in the fourth column of the above table 2 are introduced into a turboemulsifier and mixed together.
  • the turboemulsifier is heated up to a temperature of about 65°-70°C, so that the compounds in the turboemulsifier melt, and in the mean time the compounds are mixed. Complete melting of the compounds has to be achieved, so that a better mixing can be obtained.
  • Phase "B” A further turboemulsifier is heated up to a temperature of about 75°-80°C.
  • the compounds having the value "B” in the fourth column of the above table 2 are introduced in the further turboemulsifier, mixed together.
  • both the turboemulsifier and the further turboemulsifier are closed, and operated so that the respective compounds in the turboemulsifier and in the further turboemulsifier could be mixed and homogenized. Therefore, a vacuum pump, connected to the turboemulsifier is operated, and the compounds in the further turboemulsifier are poured into the turboemulsifier, i.e. compounds of phase "B" are poured in the compounds of phase "A".
  • the turboemulsifier is operated for few minutes so that the compounds of phase "A" and of phase “B” mix and homogenize together, the real mixing of the mixture can be checked and, if necessary, the turboemulsifier may be operated again. After a desired mixing of the mixture has been obtained, the vacuum pump is operated, and the turboemulsifier is cooled down to a temperature of about 45°C-50°C.
  • the vacuum pump is switched off and the compounds having the value "C" in the fourth column of the above table 9 are introduced into the turboemulsifier .
  • the turboemulsifier and the vacuum pump are both operated so that the compounds can be mixed and homogenized together, and the turboemulsifier is cooled during the homogenizing, down to a temperature of about 20°-30°C.
  • Such a temperature value is maintained for a certain time interval during which the compounds are continuously mixed.
  • the product may be poured out form the turboemulsifier and analyzed. Analysis carried out have been demonstrated that the product is very stable over time and can be packed in subsequent packing operations and stocked without any risk of separations of the single compounds of the product.
  • the product obtained is an emulsion containing the composition having the general formula AO x - (L-Me n+ ) x and additives, and other active principles, that can be used for obtaining topical-treatment products.
  • “Bactercline ulcer” is in a form of a cream that can be used for treating many skin ulcers, and in particular decubitus ulcers . Owing to the very limited dimension of the composition having the general formula AO x - (L-Me n+ ) ⁇ and the features thereof, an emulsion having very homogenous features is obtained.
  • the compound having the general formula AO x - (L-Me n+ ) ⁇ may for example used a compound containing titanium dioxide (TiO 2 ) as AO x , silver perchlorate (Ag + ClO 4 " ) as Me n+ and a bifunctional ligand L suitable for bond both the titanium dioxide and the silver perchlorate.
  • 2 g of the compound having the general formula AO x - (L-Me 11"1" ) ! contain 1.998g of TiO 2 , 0.0084g of AgClO 4 , and 0.0062g of of 4-mercaptophenyl boronic acid as bifunctional ligand L.
  • a quaternary ammonium salt is also present, i.e. benzalkonium chloride that enhance the antibacterial, antimycotic, antimicrobial, antiviral properties of "Bactercline ulcer". Similar "Bactercline ulcer” preparations may also be obtained using as bifunctional ligand L 6-mercaptonicotinic acid, and/or 11-mercaptoundecanoic acid, and/or mercaptosuccinic acid.
  • the "Bactercline ulcer” is a creamy, odourless emulsion, a water-in-oil-in water emulsion, having a white colour, with a density of about 0.995-1.005 g/cm 3 , and a viscosity of about 50,000-60,000 centipoise
  • the creamy emulsion obtained may be spread on the skin, preferably twice a day, owing to the physical features thereof the cream may be spread very easily, and forms on the skin of a user a protective layer, that is invisible and thus not unsightly, and that disinfect the skin allowing the ulcers to be treated.
  • the cutaneous tolerance of "Bactercline ulcer” has been tested on 50 adult volunteers, applying a 48-hours "Single patch test” under dermatological control.
  • the volunteers comprises 45 women and 5 men, aged between 18 and 65 years, average age 40 years, have normal skin and correspond to inclusion and non-inclusion criteria defined by DERMASCAN Group. Inclusion criteria specified that the volunteers had given their informed written consent, had no previous experience of intolerance or allergic reactions to cosmetic products, belonged to phototype I to III.
  • Non inclusion criteria specified that the persons having the following features are not included as volunteers in the study: pregnant or nursing women, or women planning to be pregnant during the study, persons having cutaneous pathology
  • the product was applied on the scapular part of the back, using patch test of the type "Finn Chambers ®" 8mm (50mm 2 ) of the occlusive type, using a dose of product for each patch test of 25 ⁇ l of the product in pure state.
  • D dryness
  • Rl roughness
  • T thickness
  • R2 reflectivity
  • a cutaneous reaction may be erythema and/or oedema, in case of presence of both erythema and oedema, the score of both erythema and oedema reactions were added.
  • M.I.I was calculated for "Bactercline ulcer” either 30 min after the spreading of "Bactercline ulcer” on the skin of the volunteers, and 24-hours after the spreading. Both the tests show a M.I.I, value for "Bactercline ulcer” of 0.00, therefore the cream produced is a non-irritating product .
  • the study has been carried out from 17/07/06 to 20/07/06 and from 24/07/06 to 27/07/06 by the clinical Unit PROCOS, Warsaw, Tru.
  • the study was conducted according to the Good clinical Practice Guidelines from FDA (FR of 08/08/1978 Part V - Decree Nr. 77N-0278), EEC (Directives Nr. 91/507 and III 3976/88 of 11/07/1990) and to the ministry of health of the French Republic.
  • the study was conducted according to Standard Operating Procedures and the Protocol defined by the sponsor. All the test events recorded during the study were reported. Controls on data veracity and conformity to the protocol were conducted and confirmed by persons participating in the study.
  • Tests have been conducted according the standard procedure described in "European Standard EN14476, May 2002 (phase 2 ; step 1) edited by European Committee for standardization to evaluate the virucidal activity of "Bactercline ulcer".
  • a certain quota of a viral suspension is added to "Bactercline ulcer” both in "clean state”, i.e. in a water solution containing 0.3 g/1 of bovine albumin, and in "dirty state”, i.e. in a water solution containing 3.0 g/1 of bovine albumin and 0.3 ml of erythrocytes.
  • FCS Fluorescence Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Suppression Supus
  • the virucidal activity was evaluated calculating the ID 50 , i.e. the dilution of the viral suspension that causes cytopathic effects in 50% of the samples, as according to the

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Abstract

A coating product comprises a composition having the general formula AOx- (L-Men+)i, wherein AOx is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (O) bonded to the metal (A) atom, Men+ is a metal ion, L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AOx) and the metal ion (Men+), and i is the number of (L-Men+) groups bound to the metal oxide AOx; the value of the parameter i depending on various factors, such as the size of the nanoparticle of AOx, the nature of the, molecule L.

Description

Material, item and products comprising a composition having anti-microbial properties
The invention relates to nanomaterials, nanomaterial products, material and items comprising nanomaterial composition, such as for example plastics, fabrics, tissues and paints.
Moreover, the invention relates to nanomaterials, nanomaterial products, material and items comprising a nanomaterial composition having antibacterial, antimicrobial, antiviral, antimycotic, germicide, photo-remediating properties .
Furthermore, the invention relates to a product for topical use having antibacterial, antimicrobial, antiviral, antimycotic, germicide properties.
Contagious diseases spread very fast and in a very simple manner between users of public buildings such as schools, swimming pools, theatres, gymnasiums, or also buses, trains, thus giving rise to epidemic diseases.
It is, therefore, very important to avoid the proliferation of bacteria, or fungi, or other microorganisms, so as to avoid spreading infections or other diseases to the different users of such facilities.
Moreover, for certain types of person the contagion could be very dangerous, for example for newborn babies, or old persons, or patients in hospitals.
It is, thus, necessary to provide in public facilities conditions that prevent contagion between the different users of the public facility.
It is, furthermore, necessary to provide wall, and/or floor, and/or furniture coatings, allowing preventing the spreading of infections.
Furthermore, it is very important to restore hygienic conditions, if necessary, and to maintain such hygienic conditions in public facilities.
Sometimes, it is very difficult, or also almost impossible to effectively restore hygienic conditions in public facilities both because of the complexity of sanitization methods that sometimes require the evacuation of the public facility, and because of the ineffectiveness of the sanitization methods. It is also important that each surface, or zone of public facilities has hygienic conditions to prevent non-hygienic zones or surfaces acting as centres for bacteria proliferation that in turn would spread within very short period of time in almost all the public facility. Furthermore, air-conditioning systems could contribute to spreading infections to all the users of a public facility by circulating the air.
Furthermore, in some industries, for example in the food industry, it is necessary to avoid bacteria proliferation in order to maintain hygienic conditions into the products processed into the industry, for example a food product. In farms, and in slaughterhouses, bacteria proliferations are, on the one hand very common, and on the other hand it is very important to limit and avoid such proliferations. In agriculture, it is often necessary to treat plants, or fruit trees, or vegetables, or also flowers, with specific products to eliminate bacteria, or fungi or other microorganisms, and to avoid a proliferation thereof that would adversely affect the quality of the vegetables or of the fruit, or would compromise the entire harvest of the farmer . Moreover, it is necessary to use on the one hand a product that is efficacious against the specific bacteria, and possibly against many different bacteria, or microorganisms, and on the other hand to use a product that is non-polluting both for the environment and for the fruit or vegetable treated with the product.
Known products are often inefficacious against many microorganisms, therefore many different products have to be used, and also known products are often polluting both for the environment and for the product for which they are used. Moreover, it is necessary to clean thoroughly public buildings, or industries, or hospitals, slaughterhouses for removing bacteria, but known detergents are often inefficacious in removing all the bacteria present in such facilities .
Moreover, when possible contagion is suspected, a person has to wash himself to remove bacteria, or other infective microorganisms, this necessity arises, for example, for doctors or those working in hospitals.
Moreover, in order to prevent any subsequent bacteria growth and/or proliferation the necessity arises to produce antibacterial materials that also maintain this property over time.
It is also important, for such a material to have an almost homogeneous structure so that no bacteria proliferation centre can develop into the structure of such a material. Moreover, certain diseases, mainly cutaneous diseases, are very widespread and although not fatal, such diseases are however unpleasant for the persons affected thereby. For example, acne is very widespread, mostly among adolescents, and adolescents affected by acne often feel very uneasy and have problems relating to others. Moreover, it is very difficult to treat acne so as to make the pustules disappear from the skin of a person affected by acne, and most of all make the pustules disappear without leaving any scares. Known products are not very efficacious, and the pustules due to the acne remain on the skin of the affected person for a very long period of time, and also the acne contagion may also spread to other zones of the skin that were previously not affected by acne. Furthermore, known products do not allow scars due to acne to be avoided.
Such scars are unsightly, also the scars are mainly on the skin of the face and therefore may not be hidden with clothes or scarves, and have to be thermally treated to be eliminated. Therefore such scares cause many problems mainly for relations with other persons. Similar problems may arise for a person affected by Herpes virus .
Such virus creates painful and unsightly vesicles, particularly in the skin of a face of a person. Such vesicles may create many problems for the relationships of a person affected thereby.
Moreover, since the vesicles are caused by a virus, it is very important to avoid any contagion by the virus of other zones of the skin of an affected person previously free of vesicles, and also to avoid any contagion of other persons.
Also in case of burns or other irritations, or inflammations of the skin, or also in the case of excoriations, or abrasions, or ulcers, such as decubitus ulcers, it is important to provide a topical product that can be applied to the affected area of the skin for efficaciously treating the disease of the affected area.
Often, known products are inefficacious for treating such diseases, and/or require a very long application time for showing the first results of treating the skin affection, and/or are too aggressive for the skin of a patient.
Moreover, often on the affected skin infections grow up due to external microbes.
The ulcers, excoriations, etc. may be infected by external microbes and the recovery becomes slower and very strong medicine have to be taken in order to try treating the infection .
The need thus arises to provide a new product for topical use that is efficacious in treating the aforementioned cutaneous affections, and that on the other has a good cutaneous tolerance, and that may form an efficacious barrier against external microbes, so avoiding any infection on the affected skin .
Moreover a cicatrizing product is often required that has a good cutaneous compatibility and is also efficacious in cicatrizing the skin and avoiding any external contagion to the wound to be cicatrized. Furthermore, many persons, suffer because they smell of sweat and/or because have body odour, and have many problems in relationships with other persons.
The need thus arises for a deodorizing product that is efficacious in deodorizing, that has a good cutaneous tolerance, and that is also efficacious against the microbes responsible for the bad body odour.
An object of the invention is to improve known coatings, such as for example, tiles, panels, carpeting, rugs, and linoleum coatings, known furniture, known materials.
Another object is to provide coatings, such as for example, tiles, panels, carpeting, rugs, linoleum coatings, furniture, materials, having antibacterial, antimycotic, antiviral, anti-pollution, self-cleaning properties. Still another object is to improve known cleansing products. Another object is to provide cleansing products having antibacterial, antimycotic, antiviral properties. Still another object is to improve known painting products. A further object is to provide a painting product having antibacterial, antimycotic, antiviral, anti-pollution, self- cleaning properties.
A further object is to improve the properties of known items. Still further object is to provide items having antibacterial, antimycotic, antiviral, anti-pollution, self- cleaning properties.
Still further object, is to provide filter means, in particular to be used in air-conditioning systems, having antibacterial, antimycotic, antiviral, anti-pollution, self- cleaning properties. Another object is to provide surgical instruments having antibacterial, antimycotic, antiviral properties. Still another object is to provide sanitary napkin means and/or linen means having antibacterial, antimycotic, antiviral properties. A further object is to improve known topical-treatment means, such as cream means, gel means, or powder means for topical use . Another object is to provide topical-treatment means having antibacterial, antimycotic, antiviral properties.
Still another object is to provide topical-treatment means for treating acne diseases. Still another object is to provide topical-treatment means for treating herpes diseases.
Still another object is to provide topical-treatment means for treating skin ulcers, and in particular bedsores, or decubitus ulcers. A further object is to provide topical-treatment means for treating cutaneous irritations, and/or inflammations, and/or abrasions, and/or excoriations, and/or burns.
A further object is to provide topical cicatrizing means for cicatrizing the skin of a user thereof. Another object is to provide a lenitive topical-treatment means for relieving topical affections.
A further object is to provide deodorizing means for topical use for deodorizing the skin of a user.
According to a first aspect of the invention, there is provided a coating product comprising a composition having the general formula AOx- (L-Men+) x .
According to a second aspect of the invention, there is provided a method for obtaining coating means comprising adding a coating product with a composition having the general formula AOx- (L-Men+) x .
According to a third aspect of the invention, there is provided the use of a coating product comprising a composition having the general formula AOx- (L-Men+) ± for reclaiming a surface. AOx is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (0) bound to the metal (A) atom;
Men+ is a metal ion, having antibacterial, antiviral, antimycotic activity; L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AOx) and the metal ion (Men+) , and i is the number of (L-Men+) groups bound to the metal oxide AOx, and the value of the parameter i depends on various factors, such as the size of the nanoparticle of AOx, the nature of the molecule L.
Owing to these aspects of the invention it is possible to remove bacteria, or other undesired and/or dangerous microorganisms from a surface only by applying such a coating product to the desired surface, so obtaining a hygienic surface, and conferring such properties to the treated surface . It is also possible to remove pollution, both organic, and inorganic, from a surface only by applying such a coating product to the desired surface. A self-cleaning surface can also be obtained.
Moreover, such a coating product maintains antibacterial, antiviral, antimycotic properties over time, avoiding any subsequent bacteria proliferation on the treated surface.
Therefore a surface can be obtained, for example a wall of a building, of a room, that maintains over time the antibacterial, antiviral, antimycotic properties. The need for subsequent treatments for reclaiming antibacterial properties is therefore avoided.
Such coating product maintains also self-cleaning properties; therefore, it is possible to obtain a self-cleaning surface, avoiding the necessity of subsequent treatments for removing pollution therefrom. Further, in case of necessity, it is possible to restore the properties of the coating product, in case for example of depletion of the metal ion(s), for example by wetting such a coating product with an alcoholic solution containing the same metal ion(s) present into the composition having the general formula AOx- (L-Men+) x .
Bacteria proliferation and spreading of infections are avoided on surfaces treated with such a coating product. Moreover, the very limited particle size of the composition having the general formula AOx- (L-Men+) ±ι allow finely disperse such composition into the structure of the coating product, and therefore a coating product having homogeneous properties can be obtained. Moreover, with such a coating product can be obtained homogeneous film that would homogeneously cover a surface on which such coating product is applied.
Therefore, on surface treated with such a coating product possible bacteria proliferation or growth centre cannot be found.
Furthermore, metal or metalloid oxide AOx adhere to any different suitable substrate, and in case, by further adding a particular additive to the coating product, it is possible to obtain a coating product that can be suitably applied to several different substrates, such as for example wood, plastic, glass, metals, ceramics, cement, and internal and external building surfaces. Further, such coating product has antibacterial, anti- pollution activity also in absence of solar light, or of any other light source, and can therefore be applied to any desired substrate assuring hygienic conditions thereof. In case, before applying such a coating product to the desired surface, a primer can be applied on the surface so as to enhance the adhesion of the coating product and to protect the surface.
In a version, the coating product can comprise a painting product . In case pigment means, and/or binder means, and/or filler means, and/or diluting means, and/or additive means, may be mixed to the painting product for obtaining a painting product having the desired features, such as for example, density, colour, consistency, etc., and for obtaining a paint substrate having the desired propertied such as for thickness, colour, brightness, or opacity, etc..
Moreover, the composition AOx- (L-Men+) x can be used for obtaining suspensions either in aqueous or in other solvents, for example polar solvents, therefore different kind of a coating products suitable for being applied to different kind of surfaces can be obtained.
For example, such a coating product can be used for coating plastics, ceramics, synthetic materials, natural rubber, synthetic rubber, wood, natural stone, marble, metal, aluminium, iron, glass, cement, linoleum, textiles, carpeting, rugs, etc., provided with antibacterial, antimicrobial, anti-pollution, properties. It is also possible to obtain an anti-pollution coating product allowing organic and inorganic pollution to be removed form a surface on which such coating product is applied, and/or from a medium contacting such coating product, and avoiding any pollution, or dirty deposition thereon.
By suitably choosing the solvent of the coating product, it is also possible to obtain transparent coating product that could be applied on to a desired surface without altering the aesthetical appearance thereof. Therefore such a coating product could be applied for example, on statues, aesthetical creations, external surface of building that are located outside, and, therefore subjected to air pollution. Further, by adding a desired pigment it is possible to obtain a coloured coating product.
Further, suspensions of the composition AOx- (L-Men+) x are stable over time, and therefore coating products that are stable over time can be obtained, avoiding the need to mix the components of the coating product only just before applying such coating product.
Moreover by adding a suitable pigment a stain can be obtained, that can be subsequently in turn used for obtaining a painting product. It is also possible to obtain material provided with a coating product conferring to said material antibacterial, antiviral, antimycotic, self-cleaning, photocatalytic, anti- mildew properties.
Since the coating product according to the invention may be applied on to any desired materials, a very wide range of material with such properties may be obtained. According to a fourth aspect of the invention, there is provided a product comprising a base material and a composition having the general formula AOx- (L-Men+) x . According to a fifth aspect of the invention, there is provided a method for producing a material wherein coating said material with a coating product comprising a composition having the general formula AOx- (L-Men+) x it is provided for. According to a seventh aspect of the invention, there is provided a method for producing a product comprising mixing with a base material of said product a composition having the general formula AOx- (L-Men+) x .
According to these aspects of the invention, it is possible to obtain materials and products provided with antibacterial, antiviral, antimicrobial, photocatalytic properties, that can be thus used for obtaining items with the aforementioned properties .
Self-cleaning materials and products can further be obtained. A composition having the general formula AOx- (L-Men+) ± is suitable for being applied to, or mixed with, in case diluted with suitable solvents, any desired materials, therefore many different materials and products with antibacterial properties can be obtained.
For example, such a composition can be used for obtaining plastics, ceramics, synthetic materials, natural rubber, synthetic rubber, wood, natural stone, marble, metal, aluminium, iron, glass, cement, linoleum, textiles. Furthermore, materials with very homogeneous properties can be obtained. Such a composition may be mixed to a base material in flowable state obtaining a product having the aforementioned properties .
Such a composition can further be mixed with a desired base material during the preparation process of a product, for example can be added to melt plastics, or glass intimately mixing with the structure of the plastics.
It is possible to obtain plastics, or glass material having a very homogeneous structure, in which structure the composition having the general formula AOx- (L-Men+) x is very homogeneously mixed, and therefore antibacterial properties are homogeneously present in such materials.
Materials and products obtained have no bacteria proliferation centre and have very high hygienic conditions. Such materials can be used for making object, items, coating means provided with antibacterial properties.
According to an eighth aspect of the invention, a cleansing product is provided comprising a composition having the general formula AOx- (L-Men+) x .
According to a ninth aspect of the invention, a method is provided for preparing cleansing means comprising adding a cleansing product with a composition having the general formula AOx-(L-Me^)1. According to these aspects of the invention, it is possible to obtain a cleansing product having antibacterial, antimicrobial, antiviral, antimycotic, anti-pollution properties that can be used for cleaning a desired surface, reclaiming hygienic properties thereof. Such a cleansing product can be used for example for cleaning floors, or walls in hospitals, schools or other public facilities, for cleaning bathrooms, public baths, showers, so avoiding bacteria proliferation. A cleansing product efficacious against many microorganisms such as for example: HSV-I (Herpes Simplex Virus-1) , Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherica CoIi, Salmonella enteridis Dl, Listeria monocytogenes, Candida albicans, Aspergillus niger, may be obtained.
In a version, said cleansing product comprises surfactant means for improving the removal of dirty, and/or abrasive means for improving the removal of dirty, and/or pH modifying means for improve the efficacy of the cleansing, and/or water softener means for counteracting the hardness of the water, oxidant means for bleaching, non-surfactant means for keeping dirty in suspension, enzyme for digesting proteins, fats, or carbohydrates in dirty, or for modifying fabric fel, foaming modifying means, optical brightener, and/or colour means, and/or perfume means, and/or essence means for improving the removal of dirty, or the efficacy and the performances of the cleansing product.
By further adding further suitable additives a cleansing product suitable for cleaning skin or hair, can be obtained. In a version, the cleansing product further comprises sodium laureth sulfate, and/or glycol distearate, and/or natural oil means, and/or coconut oil, and/or inseed oil, and/or tocopherol, and/or pantothetic acid.
Such a cleansing product would remove dirty from the skin or hair, and also would remove bacteria thereof, so avoiding proliferation of certain diseases. According to a tenth aspect of the invention a sterilising product is provided comprising a composition having the general formula AOx- (L-Men+) x .
According to a eleventh aspect of the invention a method for preparing a sterilising product comprising adding a composition having the general formula AOx- (L-Men+) ± there is provided for.
According to a twelfth aspect of the invention, a method is provided for sterilising object comprising bringing said object into contact with a sterilising product comprising a composition having the general formula AOx- (L-Men+) x .
According a thirteenth aspect of the invention, a method is provided for sterilising surgical instruments comprising bringing said surgical instruments into contact with a sterilising product comprising a composition having the general formula AOx- (L-Men+) x .
According to a fourteenth aspect of the invention there is provided a method for obtaining surgical instruments comprising at least partly coating said surgical instruments with a coating product with a composition having the general formula AOx- (L-Me^)1.
Owing to these aspects, it is possible to obtain surgical instruments that maintain antibacterial, antiviral, properties over time and that do not need to be deep sterilised between two different uses.
It is also possible to obtain a very efficacious sterilising product . According to a fifteenth aspect of the invention, a biocide product is provided comprising a composition having the general formula AOx- (L-Men+) x .
According to a sixteenth aspect of the invention, a method is provided for preparing biocide means comprises adding a biocide product with a composition having the general formula
AOx- (L-Me^)1.
According to a seventeenth aspect of the invention, the use of a biocide product comprising a composition having the general formula AOx- (L-Men+) lr there is provided for. Owing to these aspects of the invention, it is possible to obtain a biocide product that is efficacious for removing several different organisms, such as bacteria, fungi, sponges, and mildews.
It is also possible, to obtain a biocide product that could be spread on the desired surface either by spraying, or be applied to the desired surface.
It is also possible, to obtain a non-polluting biocide that could cover almost homogeneously the surface to which it is applied, therefore removing almost completely any bacteria or microorganisms present on such surface, and avoiding almost completely any subsequent proliferation thereof.
It is also possible to obtain a biocide product that is very efficacious for removing bacteria as, for example
Pseudomonas, Erwinia amilovora , Xanthomonas campestris, fungi, from plants, flowers, trees.
It also possible to obtain a non-pollution biocide product that can be used in agriculture without any limitation due to the environmental laws.
According to an eighteenth aspect of the invention, a prosthesis product is provided comprising a composition having the general formula AOx- (L-Men+) ± . According to a nineteenth aspect of the invention, there is provided a method for preparing a prosthesis means comprising at least partly coating said prosthesis means with a coating product comprising a composition having the general formula AOx-(L-Me^)1.
According to a twentieth aspect of the invention, there is provided a method for preparing prosthesis means comprising mixing prosthesis material with a product comprising a composition having the general formula AOx- (L-Men+) x . Owing to these aspects of the invention, it is possible to obtain prosthesis means that avoid any bacteria proliferation, and therefore infections to the patient. Rejection phenomena would be also limited or avoided, and therefore further troubles to the patient, due for example to a subsequent implantation of a new prosthesis, may be avoided.
According to a twenty-first aspect of the invention, there is provided filter means provided with a coating product comprising a composition having the general formula AOx- (L- Men+K.
According to a twenty-third aspect of the invention, there is provided a method for preparing filter means comprising at least partly coating said filter means with a coating product comprising a composition having the general formula AOx- (L- Men+K.
Owing to these aspects of the invention, it is possible to obtain filtering systems, such as for example air- conditioning systems that would do not contribute to spreading infections, but remove any bacteria or other microorganisms, or pollution from the air circulating therein .
Air-circulating systems improving the quality of the air in a room or in a building can thus be obtained. According to a twenty-fourth aspect of the invention, there is provided a method for preparing sanitary napkin means comprising mixing a product having the general formula AOx- (L-Me11 ) ! to absorbent material means of said sanitary napkin means .
According to a twenty-fifth aspect of the invention, there is provided a method for obtaining sanitary napkin means comprising applying a product having the general formula AOx-
(L-Me11^1 to said sanitary napkin means.
According to a twenty-sixth aspect of the invention, there is provided a sanitary napkin product comprising a composition having the general formula AOx- (L-Men+) x . According to a twenty-seventh aspect of the invention, there is provided a method for sanitizing sanitary napkin means comprising bringing said sanitary napkin means into contact with a product having the general formula AOx- (L-Men+) ±.
According to a twenty-eighth aspect of the invention, there is provided a method for sanitizing linen means comprising bringing said linen means into contact with a product having the general formula AOx- (L-Men+) x .
Owing to these aspects of the invention, it is possible to obtain antibacterial sanitary napkin means and linen means avoiding any proliferation of bacteria, fungi, virus, thereon .
It also possible to avoid any bacteria proliferation in dustbins, or container means, into which dirty sanitary napkin means are collected. This is particularly important in certain facilities where there are many users, for example, hospitals, or hospices, between whom different diseases could spread.
It possible to avoid any bacteria proliferation in linen baskets, or container means in which dirty linen, such as bed linen, or towels, are collected before being washed.
This is particularly important in certain facilities for example, hospitals, or hospices where there are many users, between whom different diseases could spread.
According to a twenty-ninth aspect there is provided the use of a composition with the general formula AOx- (L-Men+) x for obtaining a topical-treatment product for treating acne diseases . According to a thirtieth aspect of the invention, there is provided the use of a composition having the general formula AOx- (L-Men+) ! for a obtaining topical-treatment product for treating herpes diseases. According to a thirty-first aspect of the invention, there is provided the use of a composition having the general formula AOx- (L-Men+) ! for a obtaining topical-treatment product for treating skin ulcers, and in particular decubitus ulcers. According to a thirty-second aspect of the invention, there is provided the use of composition a having the general formula AOx- (L-Men+) x for obtaining a topical-treatment product for treating skin irritations, and/or skin inflammations, and/or skin abrasions, and/or skin excoriations . According to a thirty-third aspect of the invention, there is provided the use of a composition having the general formula AOx- (L-Men+) ! for obtaining a lenitive topical-treatment product . According to a thirty-fourth aspect of the invention, there is provided the use of a composition having the general formula AOx- (L-Men+) x for obtaining a cicatrizing topical- treatment product for cicatrizing the skin of a user of said cicatrizing product. According to a thirty-fifth aspect of the invention, there is provided the use of a composition having the general formula AOx- (L-Men+) ! for obtaining a burn topical-treatment product for treating burns on the skin of a user of said topical- treatment product. By suitably choosing the compounds in the composition having the general formula AOx- (L-Men+) ± topical-treatment products efficacious against many different diseases may be obtained, moreover, topical-treatment products having antiviral, antibacterial, antimicrobial, antimycotic may be obtained. According to a thirty-sixth aspect of the invention, there is provided the use of a composition having the general formula AOx- (L-Men+) ! for obtaining a topical-treatment product for treating diseases due at least by one of the following microbes: HSV-I (Herpes Simplex Virus-1) , Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherica CoIi, Salmonella enteridis Dl, Listeria monocytogenes, Candida albicans, Aspergillus niger.
Preferably the composition having the general formula AOx- (L- Me11^1 further comprises a quaternary ammonium salts for enhancing the antiviral, antibacterial, antimicrobial, antimycotic properties of the topical-treatment means. According to a thirty-seventh aspect of the invention, there is provided a method for obtaining a topical-treatment product for treating acne diseases comprising adding a composition having the general formula AOx- (L-Men+) x . According to a thirty-eighth aspect of the invention, there is provided a method for obtaining a topical-treatment product for treating herpes diseases comprising adding a composition having the general formula AOx- (L-Men+) x . According to a thirty-ninth aspect of the invention, there is provided a method for obtaining a topical-treatment product for treating skin ulcers, and in particular decubitus ulcers, comprising adding a composition having the general formula AOx- (L-Me11^1.
By suitably choosing the compounds in the product having the general formula AOx- (L-Men+) ± topical-treatment products efficacious against many different diseases may be obtained, moreover topical-treatment products having antiviral, antibacterial, antimicrobial, antimycotic properties may be obtained. According to a fortieth aspect of the invention, there is provided a method for a obtaining topical-treatment product for treating diseases due at least by one of the following microbes: HSV-I (Herpes Simplex Virus-1) , Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila , Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherica CoIi, Salmonella enteridis Dl, Listeria monocytogenes, Candida albicans, Aspergillus niger, comprising adding a composition having the general formula AOx- (L-Men+K.
The composition having the general formula AOx- (L-Men+) x may be added to any known topical-treatment products to thus obtain topical-treatment products for example in form of cream, or gel, or powder, means having antibacterial, antimicotic, virucidal, antimicrobial properties. For example such composition may be added to a common daily, or night cream, or to a moisturizing cream, thus conferring the aforementioned properties thereupon.
Owing to these aspects of the invention, it is possible to obtain topical-treatment products having antiviral, antibacterial, antimicrobial, antimycotic properties, together with other curative properties. Therefore very efficacious topical-treatment products may be obtained.
In fact, the antiviral, antibacterial, antimicrobial, antimycotic properties allow the curative properties of the topical-treatment products to be enhanced since any microbial proliferation growth is avoided, and any spread of the contagion to different areas of the skin is also avoided, and also any external contagion is also avoided.
Therefore, any infection of the skin is avoided and the curative process is more efficacious and faster than usual. Therefore very curative topical-treatment products efficacious for example against burns, irritations, inflammations, excoriations, and abrasions of the skin of a user may be obtained. Preferably the topical-treatment product comprises cream means, gel means, and/or powder means.
Moreover, by suitably choosing the elements in the composition having the general formula AOx- (L-Men+) ± may be obtained a product compatible and thus mixable with any physical form of the cream means, for example emulsions, gels, suspensions, foams, microbeadlets, microspheres, granules, microgranules, multiple emulsions, e.g. water-in- oil-in-water emulsions. Owing to the composition and the dimensions of the composition having the general formula AOx- (L-Men+) lr very homogeneous topical-treatment products may be further obtained. Moreover adding the composition having the general formula AOx- (L-Men+) ! does not require further additional step or particular precautions in the known processes for preparing topical-treatment products. Therefore, by simply further providing the adding phase for adding the composition having the general formula AOx- (L- Me11^1 known processes for producing topical-treatment products may be modified in order to produce topical- treatment products having antibacterial, antimicrobial, antimycotic, virucidal properties. According to a forty-first aspect of the invention, it is provided a deodorizing product comprising a composition having the general formula AOx- (L-Men+) x .
In a version said deodorizing product is in powder form. In a further version said deodorizing product is in spray, and/or cream form, and/or gel form, and/or aerosol form.
Owing to the very limited dimension of the composition having the general formula AOx- (L-Men+) lr deodorizing product having very homogeneous properties may be obtained. According to a forty-second aspect of the invention, it is provided the use of a composition having the general formula AOx- (L-Men+) ! for obtaining a deodorizing product. Owing to the properties of the composition having the general formula AOx- (L-Men+) ± it is possible to obtain very efficacious deodorizing products, and also deodorizing products having antibacterial, antimicrobial, antimycotic, virucidal properties.
By suitably choosing the compounds in the composition having the general formula AOx- (L-Men+) x it is possible to obtain deodorizing products having a great cutaneous compatibility, a great efficacy in deodorizing the skin of a user thereof, and also a great efficacy in avoiding any microbial growth. In the general formula AOx- (L-Men+) lr AOx may be for example titanium dioxide (TiO2) , zinc oxide (ZnO) , stannic oxide
(SnO2) , zirconium dioxide (ZrO2) , and colloidal silica (SiO2) ;
Men+ may be for example a transition metal ion, for example Ag+ Cu++.
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 AOx oxide, and second functional group binding the Men+ ions.
The first functional group may be chosen in a group comprising: carboxyl (-COOH) (or carboxylate) , phosphonic (- PO3H2) (or phosphonate) , or boronic (-B(OH)2) (or boronate) , dipyridyl group, terpyridyl group. The second functional may be chosen in a group comprising: Cl", Br", I", S, CNS", NH2, N, CN" and NCS".
Preferably, said dipyridylic or terpyridylic group is substituted by a carboxyl group, more preferably in a para position with respect to the pyridine nitrogen. If more than one dipyridylic group or terpyridylic group is present, one of these groups may be unsubstituted. The bifunctional ligands L of organic type 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 (-B(OH)2), phosphonic (-POsH2), mercaptan (-SH), and hydroxyl (- OH) ; - C6 to C18 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 (-PO3H2), mercaptan (-SH) , and hydroxyl (-0H) ; - C2 to C18 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 first functional group and the second functional group of ligand L may also be both coordinated at a metallic centre (M) of the ligand L. The metallic element of the ligand L may have a coordination of the octahedral type or different kind of coordination corresponding to tetrahedral geometry, rectangular planar, square planar geometry, bipyramidal trigonal geometry, or pyramidal geometry with a square or rectangular base, and any of the metals which are in the first, second, or third row of transition metals in the periodic table of the elements and which can give rise to stable bifunctional molecules of the type described may be used. Preferably, the transition metal coordinated by the ligand L is selected from: Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Re, Os, Ir, and Pt.
The ligand L may have a negative charge, and may form salts with cations, preferably organic cations such as tetraalkylammonium cations. By suitably choosing the atom of the metal ion Men+ and the metal or metalloid oxide AOx a composition can be obtained having antibacterial, antiviral, antimycotic, microcide, photocatalytic, anti-pollution properties. In a preferred embodiment, ion Men+ is chosen between Ag+ and/or Cu++ having antibacterial, antimycotic, antiviral, activity.
In another embodiment metal oxide AOx comprises TiC>2, preferably with titanium in Anatase form, therefore an anti- pollution, photocatalytic composition can be obtained. Such composition has particle size less than 30nm, more preferably less than 15nm. In a version quaternary ammonium salts may be added to the composition having the general formula AOx- (L-Men+) ± so enhancing the antiviral, antibacterial, antimicrobial, antimycotic properties of the composition. Quaternary ammonium salts, are positively charged polyatomic ions of the structure NR4 +X" with Rl, R2, R3, R4 being alkyl groups, and X~ a suitable anion, for example chloride anion Cl". Any or all of the R groups may be the same or different alkyl groups. Many of quaternary ammonium salts are widely used, for example chloride ammonium salts.
Quaternary ammonium salts are used for example as disinfectants, surfactants, fabric softeners, antistatic agents (e.g. in shampoo). Adding suitable quaternary ammonium salts to the composition having the general formula AOx- (L-Men+) ± it is possible to improve the stability of suspensions, or emulsions or solutions of the composition having the general formula AOx-
(L-Me11^1, and also to enhance the property thereof, increasing the antiviral, antibacterial, antimicrobial, fungicidal properties.
Moreover, by suitably choosing quaternary ammonium salts, it is also possible to enhance the cleaning properties of a detergent product. For example tetraalkylammonium salt, and/or alkylammonium salts, and/or benzalkonium chloride, may be added to the composition having the general formula AOx- (L-Men+) x . With such a composition both transparent suspensions and milky suspensions can be obtained, such a composition may be dissolved both in aqueous solvents and in polar solvents, and both in organic solvents and inorganic solvents. With such a composition, emulsions, such as creamy emulsions may be obtained. Studies have demonstrated that a formulation comprising a product having the general formula AOx- (L-Men+) x is efficacious against several different microorganisms such as for example bacteria, fungi, sponge, mildews, and also for removing organic and inorganic pollutions.
For example efficaciousness against HSV-I (Herpes Simplex
Virus-1) , Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus,
Enterococcus faecalis, Escherica CoIi, Salmonella enteridis
Dl, Listeria monocytogenes, Candida albicans, Aspergillus niger has been demonstrated.
Therefore a coating product, painting means, a material, a cleansing product, a sterilising product, topical-treatment means, deodorizing means, objects, items effective in removing such microorganisms and in avoiding further proliferation thereof can be obtained.
The invention may be better understood and implemented with reference to the following examples and attached Figures in which:
Figure 1 schematically illustrates the structure of a composition having the general formula AOx- (L-Men+) ±;
Figure 2 a schematic representation of a particular composition having the general formula AOx- (L-Men+) ±;
With reference to Figure 1 there is schematically shown the structure of a composition having the general or molecular formula AOx-(L-Me^)1.
AOx is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (0) bonded to the metal (A) atom, AOx may be, for example, titanium dioxide (Tiθ2) , zinc oxide (ZnO), stannic oxide (Snθ2) , zirconium dioxide (Zrθ2) , and colloidal silica (Siθ2) •
Men+ is a metal ion, having antibacterial, antiviral, antimycotic activity, for example Ag+, Cu++ .
L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AOx) and the metal ion (Men+) , and i is the number of (L-Men+) groups bound to the metal oxide AOx; the value of the parameter i depends on various factors, such as the size of the nanoparticle of AOx, the nature of the, molecule L. Bifunctional molecules L may be organic or organometallic molecule, as in the example in Figure 2, such as complexes of the transition metals.
Ligand L may be provided with different suitable functional groups, first functional group such as carboxyl (-COOH) (or carboxylate) , phosphonic (-PO3H2) (or phosphonate) , or boronic (-B(OH)2) (or boronate) , dipyridyl group, terpyridyl group, bonding to the AOx oxide, and second functional group such as Cl", Br", I", CNS", NH2, CN" and NCS", bonding the Men+ ions.
Preferably said dipyridylic or terpyridylic group is substituted with carboxyl group, more preferably in para position with respect to the pyridine nitrogen. In the case in which more than one dipyridylic group ar terpyridylic group is present, one of these groups may be unsubstituted.
First functional group and second functional group of ligand L may also be both coordinated at a metallic center (M) of the ligand L, as in the case in Figure 2. Preferably, the transition metal coordinated by the ligand L is selected from: Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Re, Os, Ir, and Pt.
The ligand L may have a negative charge, and may form salts with cations, preferably organic cations, more preferably quaternary ammonium cations, such as tetraalkylammonium cations .
Such composition may be mixed with cationic surfactants, such as alkylammonium salts, benzalkonium chloride, that would also enhance the bactericidal activity of the composition In Figure 2, there is shown an example of composition having the general formula AOx- (L-Men+) x in which metal oxide AOx is
TiO2, ion Me+, is Ag+ and ligand L is a metallorganic molecule having the general formula Ru (H2dcb) 2 (NCS) 2, in which
(H2dcb)2, 2, 2-dipyridyl-4, 4-dicarboxylic acid is the first functional group of the ligand L and (NCS)2 is the second functional group, and the first and second functional groups are coordinated by a metal atom M of ruthenium (Ru) . As can be seen from Figure 1, several molecules of ligand L, together with several metal ions Me+, are bound to metal oxide AOx and are arranged so that almost all the surface of the and metal oxide AOx is covered by ligand L and, therefore by ions Me+.
This is due to the small dimensions if the ligand L and of the metal ion Me+, which may be of the order of picometers, therefore each molecule of metal oxide AOx can be homogeneously covered by metal ion Me+. Furthermore, owing to the very small dimensions of the molecules contained composition AOx- (L-Men+) x nanoparticles are obtained that can be added to a material and intimately mixed to it, obtaining a material, for example a plastic with homogeneous properties. For the same reason very homogeneous emulsions, or suspensions, or solutions in many different solvents may be obtained with the composition AOx- (L-Men+) x.
Such composition can be spread, or applied to a surface allowing a very homogeneous coverage and/or coating of the surface to be obtained.
Compositions having the general formula AOx- (L-Men+) x have particle size less than 40nm, preferably mess than 30nm, more preferably less than 15nm. Therefore very thin and homogenous films homogeneously covering a surface can be obtained.
Composition having the general formula AOx- (L-Men+) ± may be used for obtaining suspensions both transparent and milky, both in aqueous and polar solvents, both in inorganic and organic solvents, such suspension being stable over time. For obtaining suspension of the composition having the general formula AOx- (L-Men+) x a metal or metalloid oxide AOx is mixed with a Ligand L, and with a solution into which ion Men+ are dissolved. Oxides AOx are usually available as suspension, for example colloidal suspensions, or also in powder form.
Colloidal suspension based, for example, on colloidal silica, and/or stannic dioxide are commercially available. Suspension based on titanium dioxide and/or zirconium dioxide may be also prepared, for example as explained thereafter. The afore mentioned suspension may be transparent or opaque, or milky and would affect the colour properties of the final suspension prepared.
The suspension of the metal or metalloid oxide AOx are properly mixed with a suitable Ligand L so that a certain number of molecules of the ligand may be absorbed on the surface of a molecule of oxide AOx, as can be seen from the Figure 1, and explained in the following examples.
The number of molecules L absorbed to a molecule of the oxide AOx depends on the particular oxide AOx used.
Thereafter an alcoholic solution containing the ions Men+ of a suitable metal is mixed, so that the metal ions may be absorbed on the molecule L, as can be seen in the Figure 1.
The absorption of the ligand L on the molecule of the oxide AOx requires about 12-36 hours, whereas the absorption of the metal ions Men+ is substantially an instantaneous reaction. Thereafter stable suspensions are obtained in which the ligand L is bound both to the oxide AOx and to the metal ions Men+, such suspensions may be used for obtaining many different products, for example the products cited above and in the uses above specified. In some other cases oxide AOx in powder form may be added to a solution containing the ligand L and therefore an alcoholic solution of metal ions Men+ may be added.
In some other cases cationic surfactants may be absorbed on to oxide AOx and therefore a ligand L, preferably in suspension and/or in solution, and an metal ions Men+, preferably in alcoholic solution, may be added and mixed so that the absorption reactions may take place.
The presence of cationic surfactants may enhance the absorption of the ligand L to the oxide AOx and also the absorption of the metal ions Men+ on the ligand L. Cationic surfactants may also improve the solubility of the components into the suspensions, improving the stability thereof, and also enhance the antibacterial, antimycotic, antimicrobial properties of the suspensions obtained. After the composition having the general formula AOx- (L-Men+) x has been obtained in any desired form, for example a suspension of a composition having the general formula AOx- (L-Me11^1, such composition may be used for obtaining for example paints.
Such composition may be added to any desired known paint thus obtaining a paint having anti-bacterial, antimicrobial, antimycotic, self-cleaning, anti-polluting properties.
Otherwise, such composition may be added during a desired stage of a process for producing paint.
In case the particular solvents used in the preparation of the suspension of the composition, and or the form of the composition may be chosen in view of a compatibility with the ingredients of the particular paint that it is desired to obtain .
The same applies when a cleansing product is produced using the composition having the general formula AOx- (L-Men+) ±. In fact, the composition having the general formula AOx- (L- Men+)i may be added to a known cleansing product so obtaining a cleansing product having anti-bacterial, antimicrobial, antimycotic, self-cleaning, anti-polluting properties. Otherwise the composition having the general formula AOx- (L- Men+)i may be added to any desired stage of the process for producing a cleansing product to the ingredients of the cleansing product. Moreover by suitably choosing the form of the composition having the general formula AOx- (L-Men+) ± and/or the particular solvent (s) used for preparing a suspension thereof, a wide range of cleansing products may be obtained.
Moreover, after the composition having the general formula AOx- (L-Men+) ! has been obtained in any desired form, such as suspension, emulsion, solution, such composition may be added to the ingredients for preparing topical-treatment products, for example, a cream, a night cream, a lenitive cream or gel, a moisturizing cream or gel, obtaining a topical-treatment product having curative properties.
Such a composition may also be added to the ingredients for preparing curative topical-treatment products, for example to a burn cream, enhancing the curative properties thereof and conferring to the curative topical-treatment product antimicrobial, antibacterial, antimycotic, antiviral properties . Example 1 Transparent suspensions based on TiO2 Into a beaker there were charged 300 mL distilled H2O and 2.1 mL of a strong acid, e.g. concentrated HNO3 (65% w/w) . Over a period of 10 min, 50 mL titanium isopropoxide (supplied by Fluka) was added under stirring, by means of a dropping funnel . A white milky precipitate of TiO2 was formed.
The mixture was then heated at 80 °C for 8 to 12 hours, taking care to maintain the stirring and the temperature constant . During the heating, the precipitate redissolves, and the mixture took on an opalescent appearance.
During the phase of heating, the colloidal suspension was concentrated to a final volume of 100 to 200 mL, corresponding to a TiO2 concentration of 150-75 g/L. The nanoparticles of titanium dioxide obtained at the end of the process had a diameter in the range 6 to 15 nm.
The suspension concentrated to 100 mL was then diluted by addition of distilled water and ethanol, to give a final transparent solution (pH~2) that has a concentration of TiO2 of 1.5% and a percentage of alcohol comprised between about 10% to about 50%, preferably of about 25%.
Example 2 Transparent suspensions based on ZrO2
Into a beaker there were charged 300 mL distilled H2O and 2.1 mL of a strong acid, e.g. concentrated HNO3 (65%) .
Over a period of ca. 10 min, 76 mL zirconium tetraisopropoxide (70% in isopropanol) was added under stirring, by means of a dropping funnel. A white milky precipitation of ZrC>2 was seen to form almost immediately.
The mixture was then heated at 900C for 8 to 12 hours, taking care to maintain the stirring and to maintain constant temperature.
During the heating, the precipitate redissolves, giving rise to a milky-appearing suspension, which was concentrated to 140-280 mL, corresponding to a ZrU2 concentration of 150-75 g/L. The suspension concentrated to 140 mL was diluted with distilled water and ethanol to obtain 1.4 L of an opalescent suspension (pH~2) having a concentration of ZrU2 of 1.5% and a percentage of alcohol comprised between about 10% and about 50%, preferably of about 25%. Example 3 Opaque suspensions based on TiO2:
Neutral aqueous opaque suspensions based on titanium dioxide can be obtained by adding titanium dioxide P25 to aqueous solutions of "Triton X 100" (supplied by Fluka) . Neutral aqueous opalescent suspensions based on titanium dioxide may also be prepared from peroxytitanic acid by a modification of a procedure reported in the literature
(Ichinose, H., Terasaki, M., and Katsuki, H., 1996 J. Ceramic
Soc. Japan, 104, 715) .
In a typical preparation, 150 mL TiCl4 in 20% HCl is charged to a 1 L beaker, and 826 mL NH4OH diluted 1:9 with distilled water is added to this solution.
The pH of the resulting solution is neutral (pH=7), and titanic acid, Ti(OH)4, is precipitated. This precipitate is white and has the consistency of a gel. The precipitate is collected on a filter of porosity G3, and is washed with 750-1000 mL distilled water (until complete elimination of the chloride is achieved, as can be demonstrated by treating the liquid filtrate with AgNOs) • The precipitate comprised of titanic acid, Ti(OH)4, is collected and is suspended in 200 mL distilled water having conductivity less than 1.5 mS and having pH comprised in the interval 5-7; to this there is slowly added over a period of 20-30 minutes 92 mL of 30% H2O2.
The dissolution of the precipitate is noted, and the formation of a yellow-coloured solution containing peroxytitanic acid, of general formula [Ti2 (O) 5 (OH) x] (x~2)~, where x is in the range 3-6.
Finally the solution is heated 1 hr at 70 0C to decompose the excess H2O2, and is then autoclaved 8 hr at 120 0C. In this phase of the procedure, the peroxytitanic acid decomposes to titanium dioxide, principally in the allotropic form of anatase.
The resulting suspension of nanoparticles has a pH close to neutral, and an opaque appearance, and is stable over time. Suspensions obtained according to any one of the examples 1 to 3 or suspensions obtained in any other suitable methods and containing at least metal or metalloid oxide having formula AOx , or in any case metal or metalloid oxide having formula AOx in any other suitable form, for example in powder form, are made to react with a suitable bifunctional ligand (L) so that the ligand L is adsorbed on to the particles of the oxide AOx.
The number of molecules of ligand L absorbed on each molecule of oxide AOx depends on the features of the ligand L and of the oxide AOx. Thereafter an aqueous or alcoholic solution containing metal ions Men+, for example Ag+ or Cu2+ ions, is added so that the metal ions Men+ are absorbed on the molecule of the Ligand L, obtaining the structure shown in Figure 1. Therefore a suspension, or a solution, containing a composition having the general formula AOx- (L-Men+) ± is obtained.
A cationic surfactant may then be added to the suspension of nanomaterials functionalized with metal ions Men+, or may be independently added to or adsorbed onto the oxide AOx Example 4 Adsorption of 4-mercaptophenylboronic acid and Ag+ ions onto "TiO2 P25" (supplied by Degussa) : To a solution containing 2*105 moles of 4- mercaptophenylboronic acid dissolved in 50 mL ethanol there was added 1 g of TiO2 P25 (supplied by Degussa) . The suspension was stirred 24 hr . 4-mercaptophenylboronic acid has an absorption band at 255 nm, attributable to the π- π* transition in the phenolic ring.
This electronic absorption band permits the adsorption of the boronic acid onto the surface of the nanomaterial as a function of time to be monitored. It is known that the adsorption occurs by interaction of the boronic function with the surface of the semiconductor. The electronic absorption spectra demonstrate that the quantity of 4-mercaptophenylboronic acid adsorbed on the surface of the "TiO2 P25" reaches 35% of the initial concentration in 24 hr .
The solution was centrifuged 10 min at 4000 rpm, obtaining a clear solution, the solid was washed with 20 mL ethanol, and was then re-suspended with 50 mL ethanol under stirring. To this suspension was added 7.2*10~6 moles of a soluble silver salt, preferably silver lactate or silver acetate.
The suspension obtained was white in colour, odourless, and stable over time.
A suspension containing a composition having the general formula AOx- (L-Men+) x is obtained, in which AOx is TiO2, L is 4- mercaptophenylboronic, and Men+ is Ag+.
Example 5 Adsorption of 4-mercaptophenylboronic acid and Ag+ ions onto transparent suspensions of TiO2 obtained according to example 1 , and onto products of the firm NMTech 100 mL of a transparent solution of titanium dioxide prepared according to method (A) and containing 15% TiO2 was diluted with 100 mL distilled water and with 200 mL of a solution of 0.052 g 4-mercaptophenylboronic acid dissolved in ethanol. The suspension was stirred 24 hr, at the end of which period a spectrophotometric determination revealed that the boronic acid was completely adsorbed on the semiconductor nanoparticles . The small dimensions of the nanoparticles with respect to "TiC>2 P25" and the consequent larger surface area of the suspended matter are responsible for the complete adsorption of the bifunctional ligand. To the transparent odorless suspension there was added under stirring a stoichiometric amount (with respect to L) of a silver salt, e.g., silver lactate (0.06 g) or silver acetate
(0.05 g) .
After 1 hr of continuous stirring, there was added 10-20 mL, preferably 12 mL, of a 50% (w/v) aqueous solution of benzalkonium chloride, and the suspension was stirred for an additional 1 hr .
The concentrated suspension was then diluted with distilled water and ethanol to obtain 1 L of an opalescent suspension (pH~2) containing TiC>2 in a concentration of 1.5% and ethanol comprised between about 10% and about 50%, preferably of about 25%.
The transparent suspension was found to be indefinitely stable . A suspension containing a composition having the general formula AOx- (L-Men+) ± is obtained, in which AOx is TiO2, L is 4- mercaptophenylboronic, and Men+ is Ag+, and further comprising a quaternary ammonium salt such as benzalkonium chloride. Hereinbelow, this product will be designated as "Bactercline" , for the sake of brevity.
The same procedure may be employed to modify transparent suspensions of nanomaterials marketed by NM Tech Ltd. and designated "PSO 419", wherewith the amounts of bifunctional ligand and of silver ions are adjusted based on the amount of titanium dioxide in the product.
For example, the product "PSO-419 D2" which is similar to the product prepared according to the example 1, and which has a content of TiO2 of 2% and pH ca. 2, can be converted into an antibacterial and antiviral product using a method analogous to that described above. In particular, 50 mL of "PSO-419D2" solution containing 2% TiO2 is diluted with 2.2 mg 4-mercaptophenylboronic acid (2.05xl0~5 M), and the suspension is stirred 24 hr . To the resulting odourless solution there is added 2.05xl0~5 M silver lactate or silver acetate.
Finally, after 1 hr of continuous stirring, 8-20 mL, preferably 12 mL of an aqueous solution of dimethyl benzyl dodecyl ammonium chloride (50% w/v) is added, and the suspension is stirred for an additional period of 1 hr . The resulting transparent suspension is indefinitely stable. It should be noted that other opaque products marketed by NM Tech Ltd., such as "AT-Ol" and "AT-03", based on TiO2, can be treated according to the described methods according to the present invention, to give rise to stabile suspensions or powders which have antibacterial and antiviral activity.
For example: 50 mL of a solution of "AT-Ol" containing 1.7% TiO2 was diluted with 50 mL ethanol containing 3.8 mg of dissolved 4-mercaptophenylboronic acid (1.9xlO~5 M), and the suspension was stirred 24 hr, yielding an odourless product. Then 1.9xlO~5 M silver lactate or silver acetate was added. The resulting suspension gave rise to a fine precipitate, after a period of time.
Example 6 Adsorption of cationic surfactants onto titanium dioxide Cationic surfactants with antibacterial activity are generally adsorbable onto nanomaterials based on TiO2, ZrO2, SnO2, ZnO and SiO2.
The adsorption occurs nearly instantaneously onto negatively charged or neutral nanoparticles . In the case of suspensions of nanomaterials with basic pH, the addition of benzalkonium-type salts, such as, for example, benzyl dodecyl dimethyl ammonium chloride, or benzyl hexadecyl dimethyl ammonium chloride, or benzalkonium chloride, causes precipitation of the suspension; whereas in the case of suspensions of nanomaterials with neutral or acid pH the suspension is stable. Indirect tests of the adsorption of benzalkonium chloride on nanomaterials based on TiO2 at neutral pH employ conductimetric measurements.
The association via adsorption of the benzyl dialkyl ammonium cation on the TiO2 should predictably cause a reduction in conductivity, as was verified in the following experiment. A 50% (w/v) solution of benzalkonium chloride diluted 1:10 has a conductivity of 4.7 mS . If the volume of this solution is increased by 10 to 15 mL by addition of distilled water, the conductivity is reduced to 3.90 mS. If instead the solution is diluted by adding 5 mL of a neutral suspension of titanium dioxide prepared, according for example to the example 3, from peroxytitanic acid, or the equivalent "AT-03" product at neutral pH, the conductivity measured is 3.60 mS .
The reduction in conductivity by 300 μS is attributable to the adsorption of the cationic surfactant onto the surface of the titanium dioxide. Therefore, very stable suspension may be obtained in which the quaternary ammonium salts are absorbed in the molecule of the AOx, in this case of the TiO2.
Moreover, a single quaternary ammonium salt may be added or also a mixture of different quaternary ammonium salts, preferably a mixture of salts with the same anion, such as chloride ammonium salts.
Example 7 Adsorption of 2 ,2 ' -dipyridyl-4-carboxy-4 ' - carboxylate acid , Ag+, and Cu2+, onto "TiO2 P25" (supplied by
Degussa)
The 2-2 ' -dipyridyl-4-carboxy-4 ' -carboxylate anion acid (abbreviated "Hdcb") is produced by adding one equivalent of tetrabutylammonium hydroxide (abbreviated TBAOH) to 2,2'- dipyridyl-4, 4 ' dicarboxylic acid (abbreviated H2dcb) , which is scarcely soluble and is in solid form. The ligand in the monocarboxylate form (also called "monoprotonated form"), and as a tetrabutylammonium salt (abbreviated "TBA (Hdcb) "), can thus be solubilized in methanol or ethanol and can be adsorbed on titanium dioxide. To a solution of 1x104 moles TBA(Hdcb) in 100 mL ethanol there was added 5 g "TiC>2 P25" (supplied by Degussa) . The suspension was stirred 24 hr .
The ligand TBA(Hdcb) has an absorption band at 294 nm, due to π-π* transitions, which allows monitoring of its adsorption onto nanomaterials as a function of time.
The ligand is completely adsorbed onto the surface of the nanocrystalline substrate. It is known that the adsorption occurs by interaction of the carboxyl functions with the surface of the semiconductor.
The suspension was then centrifuged 10 min at 4000 rpm, and the solid was washed with 50 mL methanol. The nanomaterial obtained, functionalized with the ligand (abbreviated Tiθ2/TBA (Hdcb) ) , was then finally vacuum-dried at ambient temperature.
Two portions of 2 g each, of the TiO2/TBA (Hdcb) , were re- suspended in 100 mL ethanol.
To one suspension there was added 8 mg silver lactate, under stirring; and to the other suspension there was added 7 mg CuCl2.
The two suspensions had different stabilities: the suspension functionalized with copper ions, TiO2/TBA[Hdcb] /Cu2+, remained stable, while that functionalized with silver ions, TiO2/TBA [Hdcb] /Ag+, precipitated over time.
Example 8 Adsorption of organometallic ligands (L) and Ag+ ions on neutral suspensions of TiO2
Bifunctional organometallic ligands L, as previously disclosed can be anchored to neutral suspensions of titanium dioxide prepared, for example according to method of example 3, with the nanomaterials being suspended in alcohol solutions of a concentration of approximately 10~3-10~4 M of the bifunctional organometallic ligands. The suspension is stirred 12 hr, during which time the organometallic ligand L is completely adsorbed onto the surface of the nanomaterials. The addition of stoichiometric amounts of silver with respect to the ligand L, in alcoholic solution, corresponds to formation of adducts in which the silver ion Ag+ is anchored to the inorganic ligand, as illustrated schematically in Figure 1 in the case of the complex (H2dcb) 2Ru (NCS) 2 (H2dcb = 2,2' -dipyridyl-4, 4 ' -dicarboxylic acid) .
The presence of the carboxyl functions enables adsorption of the complex, and homogeneous covering of the nanocrystalline material, for a time of the order of 2-3 hr at 50 0C, and 12 hr at ambient temperature.
In a subsequent step, a silver salt, e.g. silver nitrate, silver lactate, or silver acetate, is added to the methanolic solution, in a stoichiometric ratio of 2:1 with respect to the moles of (H2dcb) 2Ru (NCS) 2. The presence of the two NCS groups allows the Ag+ ions to be instantaneously bonded as illustrated in Figure 2. Antibacterial and antiviral activity of the composition having the general formula general formula AOx- (L-Men+) ± has been tested, in particular with reference to products obtained according to any one of the examples 1 to 8.
The testing was conducted by depositing films comprised of the different nanomaterials obtained according to the afore described examples on Petri capsules in contact with a number of colonies of Escherica CoIi greater than 104 cfu (colony forming units) .
In all cases, complete mortality of the colonies was observed.
More thorough measurements were carried out according to the standards UNI-EN 1276 of April 2000 and UNI-EN 13697 of December 2001, for the product synthesized according to method of example 5 (product designated "Bactercline") , which product is transparent and thus applicable to a broader range of applications. Tests have been conducted for evaluating the bactericidal, antimycotic, virucidal properties of a solution of the product named as "Bactercline" containing a composition having the general formula AOx- (L-Men+) lr in which AOx is TiC>2, L is 4-mercaptophenylboronic, and Men+ is Ag+, and, in case, further comprising a quaternary ammonium salt such as benzalkonium chloride.
Such product may be obtained in any suitable method, for example according to the methods in examples 4, 5, 6.
The bactericidal activity of "Bactercline" has been evaluated using the method of dilution and neutralization according to standard method UNI-EN 1276 of April 2000. The following strains were used for the testing: Pseudomonas aeruginosa, Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Salmonella enteridis Dl, Listeria monocytogenes .
All of the bacterial strains tested were provided by the Department of Experimental and Diagnostic Medicine, Microbiology Section, of the University of Ferrara. The "Bactercline" product tested was diluted to 80%. The substance being tested was deemed bactericidal if for each bacterial strain at 200C after a contact time of 5 min, a reduction of vitality of at least 105 units obtained. The results obtained are reported in the following Table 1.
The obtained results indicate that in all cases a reduction in vitality of greater than 105 units was obtained.
Figure imgf000038_0001
Table 1 Based on the results obtained and the validity criteria of the tests, the "Bactercline" substance tested is bactericidal when used at a concentration of 80% (which turns out to be the maximum testable concentration) , after 5 min of contact in the presence of bovine albumin at a final concentration of 0.3%, according to the method of the standard UNI-EN 1276 of April 2000.
"Bactercline" is bactericidal also when used at a concentration of 50%, after 5 min of contact in the presence of bovine albumin at a final concentration of 0.3%, according to the method of the standard UNI-EN 1276 of April 2000, since also at such a concentration a vitality reduction more than 105 units is obtained. The bactericidal activity of "Bactercline" is therefore very high.
A surface test has also been made for evaluating the bactericidal activity of "Bactercline" according to the standard method UNI-EN 13697 of December 2001. The following strains were used in the tests: Pseudomonas aeruginosa, Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Salmonella enteridis Dl, Listeria monocytogenes, Legionella Pneumophila .
The substance being tested was deemed bactericidal against the bacterial strains provided according to the European Standard if for each bacterial strain, at 200C after a contact time of 5 min, a reduction of vitality of at least 104 units is obtained.
The results obtained are reported in the following Table 2. Such values indicate that in all cases the decimal logarithm of the antimicrobial activity was greater than 4, and therefore that "Bactercline" is a bactericidal product. Based on the results obtained and the validity criteria of the tests, the "Bactercline" substance tested under the stated test conditions is bactericidal against the tested microorganisms, when used at a concentration of 100%, after 5 min of contact in the presence of bovine albumin at a final concentration of 0.3%, according to the method of the standard UNI-EN 13697 of December 2001.
Figure imgf000040_0001
Table 2
The antimycotic, or fungicidal, activity of "Bactercline" has been evaluated using the method of dilution and neutralization according to standard method UNI-EN 1650 of
October 2000.
The following strains were used for the testing: Candida albicans, Aspergillus niger.
The strains tested were provided by the Department of
Experimental and Diagnostic Medicine, Microbiology Section, of the University of Ferrara.
The substance being tested was deemed fungicidal if, for each of the mycotic strains, at 200C after a contact time of 15 min, a reduction of vitality of at least 104 units is obtained.
The tests have been repeated for different values of the concentration of "Bactercline" , and the results obtained have been reported in table 3.
TEST MICROORGANISMS REDUCTION IN VITALITY
Concentration of
25% 50% 80% "Bactercline"
Candida albicans >1 .13xlO4 >1.13xlO4 >1 13xlO4
Aspergillus niger <1 .87x10" >1.37xlO4 >1 37xlO4
Table 3
Based on the results obtained and the validity criteria of the tests, the "Bactercline" substance tested is antimycotic against Candida albicans at concentrations of 25%, 50%, and 80%, and against Aspergillus niger at concentrations of 50% and 80% (which turns out to be the maximum concentration testable) , after 15 min of contact in the presence of bovine albumin at a final concentration of 0.3%, according to the method of the standard UNI-EN 1650 of October 2000. The antimycotic activity of "Bactercline" has been evaluated also using the surface test according to standard method UNI-
EN 13697 of December 2001.
The following strains were used for the testing: Candida albicans, Aspergillus niger.
The strains tested were provided by the Department of
Experimental and Diagnostic Medicine, Microbiology Section, of the University of Ferrara.
The substance being tested was deemed antimycotic if the logarithm of the antimicrobial activity against the microbial strains provided according to the European Standard was greater than or equal to 3, for 15 minutes of contact at
200C. The results of the tests have been reported in Table 4.
Figure imgf000041_0001
Table 4
Based on the results obtained and the validity criteria of the tests, the "Bactercline" substance tested under the stated test conditions is antimycotic against Candida albicans and Aspergillus niger, when used at a concentration of 100%, after 15 min of contact in the presence of bovine albumin at a final concentration of 0.3%, according to the method of the standard UNI-EN 13697 of December 2001. Moreover the virucidal activity of "Bactercline" has been tested.
The experiments described hereinbelow demonstrate that the product "Bactercline", in very low concentrations, has high virucidal activity against the HSV-I virus (herpes simplex virus-1) .
Various amounts of viral suspensions were prepared in modified Dulbecco medium (D-MEM) to which 1% of bovine fetal serum (BFS) had been added. A virus concentration (virus titre) of 1x10 cytolytic plaque forming units (Pfu) was used.
Different amounts of "Bactercline" were added to different samples, with pre-treatment times of 1 and 5 hr . Untreated viral suspensions were maintained as a control.
After a period of incubation at ambient temperature, all of the samples were diluted to known volumes, for determining the titres of the virus.
The viral titres of the controls and of the samples treated with "Bactercline" e were determined by the method described hereinbelow.
In determining the viral titre, the number of infectious present in 1 mL of solution may be calculated.
A method used provided for determining the number of cytolysis plaques produced by a sufficiently diluted viral suspension and placed in contact with a monolayer of cells.
In this series of experiments, renal cells of African Monkey were used (Vero) .
The cells were cultured at 37°C, in the presence of 5% of CO2 in "D-MEM" to which 10% BFS, 1% L-glutamine, and 1% penicillin/streptomycin had been added.
The determination of the titre was carried out on plates having 12 wells.
When the cultures were nearly confluent, the viral stock was diluted to known concentrations in a medium containing 2%
BFS.
For each dilution, 2 wells on the plate were inoculated.
After incubation 1 hr at 37 0C, the inoculum was drawn off and the infection was blocked by adding a medium containing 1% BFS and 2% human gamma globulin, having the function of inhibiting formation of secondary plaques.
The inoculated cultures were incubated at 37 0C for 2 days, and were monitored until the lysis plaques were visible. At this point, the cells were fixed and were stained with gentian violet. Under an optical microscope, the plaques present in the wells were counted and this count was multiplied by the dilution factor, to obtain the viral titre, in units of Pfu/mL.
The "Bactercline" product in the amount of 10 and 50 microliters was contacted with HSV-I having a viral titre of
IxIO6 Pfu.
The incubation was carried out in 1 mL of D-MEM medium to which 1% of BFS had been added.
Two different incubation times were used: 1 hr and 5 hr .
After the given incubation period, the virus was diluted to concentrations of IxIO3 and IxIO2 Pfu, and the nearly confluent cultures were inoculated.
As shown in Table 5, the cells inoculated with the virus pretreated with "Bactercline" did not have lysis plaques, for either of the pretreatment times and either of the virus dilutions .
The tests on the antiviral activity of the "Bactercline" product shows that the product has antiviral activity for direct contact with HSV-I virus even at extreme dilutions of the product, at a contact time of 1 hr .
The experiments carried out, the results of which have been represented in following table 5, demonstrated that at a level of dilution of the product of on the order of 1:100 one achieves nearly total mortality of the viral particles.
Figure imgf000043_0001
Table 5
Example 9 Method for producing a cream for topical use containing the composition having the general formula AOx- (L-
Using the composition having the general formula AOx- (L-Men+) ± many different kind of topical-treatment products for topical use may be obtained, since the composition having the general formula AOx- (L-Men+) ± may be suitably mixed with many different substances.
For example a topical-treatment cream to be used for treating acne may be obtained.
In the following table 6 the percentage content of a cream for topical use for treating acne is indicated.
Figure imgf000044_0001
Table 6 The aforementioned compounds are weighed and dosed.
A turboemulsifier is heated up to a temperature of about 65°-
700C.
Phase "A": The compounds having the value "A" in the fourth column of the above table 1 are introduced into a turboemulsifier and mixed together. The turboemulsifier is heated up to a temperature of about 70°-80°C, so that the compounds in the turboemulsifier melt.
Complete melting of the compounds has to be achieved, so that better mixing can be obtained. Phase "B": A further turboemulsifier is heated up to a temperature of about 75°-80°C. The compounds having the value
"B" in the fourth column of the above table 6 are introduced into the further turboemulsifier, mixed together.
As the compounds in the turboemulsifier and in the further turboemulsifier reach the desired temperature values, both the turboemulsifier and the further turboemulsifier are closed, and operated so that the respective compounds in the turboemulsifier and in the further turboemulsifier can be mixed and homogenized. Thus, a vacuum pump, connected to the turboemulsifier is operated, and the compounds in the further turboemulsifier are poured in the turboemulsifier, i.e. compounds of phase "B" are poured in the compounds of phase "A". The turboemulsifier is operated for a small number of minutes so that the compounds of phase "A" and of phase "B" mix and homogenize together, the real mixing of the mixture can be checked and, if necessary, the turboemulsifier may be newly operated. After the desired mixing of the mixture is obtained, the vacuum pump is operated, and the turboemulsifier is cooled down to a temperature of about 45°C-50°C.
After such a temperature value is reached, the vacuum pump is switched off and the compounds having the value "C" in the fourth column of the above table 6 are introduced into the turboemulsifier .
The turboemulsifier and the vacuum pump are both operated so that the compounds can be mixed and homogenized together, and the turboemulsifier is cooled during the homogenizing, down to a temperature of about 20°-30°C. Such a temperature value is maintained for a certain time interval during which the compounds are continuously mixed. After a given time interval has elapsed, the product may be poured out form the turboemulsifier and analyzed. Analysis carried out have demonstrated that the product is very stable over time and can be packed in subsequent packing operations and stocked without any risk of separations of the single compounds of the product.
The product obtained, referred to hereinafter as "Bactercline acne" for the sake of brevity, is an emulsion containing the composition having the general formula AOx- (L-Men+) x and additives and/or other active principles that can be used for preparing topical-treatment products. Such an emulsion is in creamy state and can be used for treating many diseases, and in particular, acne diseases. Owing to the very limited dimension of the composition having the general formula AOx- (L-Men+) ± and the features thereof, an emulsion having very homogenous features is obtained.
As the composition having the general formula AOx- (L-Men+) ± may for example be used a composition containing titanium dioxide (TiO2) as AOx, silver perchlorate (Ag+ClO4 ") as Men+ and a bifunctional ligand L suitable to bond both the titanium dioxide and the silver perchlorate.
Preferably, 2 g of the composition having the general formula AOx- (L-Me11"1") ! contain 1.998g of TiO2, 0.0084g of AgClO4, and 0.0062g of 4-mercaptophenyl boronic acid as bifunctional ligand L. A quaternary ammonium salt is also present, i.e. benzalkonium chloride .
Similar preparations may also be obtained using as bifunctional ligand L 6-mercaptonicotinic acid, and/or 11- mercaptoundecanoic acid, and/or mercaptosuccinic acid. "Bactercline acne" is a creamy, odourless emulsion, having a white colour, with a density of about 0.995-1.005 g/cm3, and a viscosity of about 50,000-60,000 centipoises. The creamy emulsion obtained may be spread on the skin, preferably twice a day, owing to the physical features thereof the cream may be spread very easily, and forms on the skin of a user a protective layer, that is invisible and thus not unsightly, and that disinfects the skin allowing the acne diseases to be treated. Spreading "Bactercline acne" twice a day on the skin affected by acne and/or herpes, skin lesions due to acne and/or herpes are healed, and any further contagion of different areas of the skin of the user is prevented.
The cream forms on the skin of a user a protective layer that has a multiple action: it protects the area of the skin lesions from any external infections, and/or microbial infections, protects such area from any external aggression due, for example, to the wind and/or sun radiation, and also prevents any contagion spreading over different areas of the skin of the user, and also any microbial proliferation over such area.
This enables a very fast regeneration of the damaged skin, and the spread of the contagion to be prevented, and enables therefore the skin diseases to be successfully treated. Such a cream may also be usefully used for treating herpes virus topical diseases. By spreading the cream twice a day on the skin affected by herpes, skin lesions due to herpes are healed, and any further contagion in different areas of the skin of the user is prevented.
The process for producing the cream is very simple and the phase of adding the composition having the general formula AOx- (L-Men+) ! does not interfere with an usual process for producing a topical-treatment product.
Therefore, similar process may be used for producing many different topical-treatment products containing the composition having the general formula AOx- (L-Men+) x and additives or active principles different from those described above .
Topical-treatment products that can be used for different topical uses and for treating many different diseases may be thus obtained. Furthermore, the composition having the general formula AOx- (L-Me11^1 may be added to many different kind of topical- treatment products, such as vanishing cream, shaving cream, anti-wrinkle cream, moisturizing cream, protective cream, daily cream, or night cream, giving to the topical-treatment product the antibacterial, antiviral, antimicotic properties. Moreover, the composition having the general formula AOx- (L- Men+)i may also be added to topical-treatment products in other forms than cream, such as for example gel, tissues soaked with active principles, wipes, patches, liquid crystals, liquid compositions with two or more distinct layers, dispersions, emulsions, suspensions, foams, microbeadlets, microspheres, granules, microgranules, microemulsions ; nanoemulsions, multiple emulsions, e.g. water-in-oil-in-water, encapsulated compositions. Moreover, the topical-treatment product produced according to the aforementioned process and containing the compounds of the aforementioned table is efficacious against the following microbes: bacteria: Pseudomonas aeruginosa, Staphylococcus aureus, Staphylococcus epidermidis, Enterococcus faecalis, Escherichia coll, Salmonella enteriditis Dl, Listeria monocytogenes, Legionella Pneumofila ; fungi: Candida albicans, Aspergillus niger; virus: Herpes virus.
Tests have been conducted to evaluate the virucidal efficacy of "Bactercline acne" against different viruses and in particular against Poliovirus and Adenovirus . Tests were conducted according to the standard procedure described in "European Standard EN14476, May 2002 (phase 2 ; step 1) edited by the European Standardization Committee to evaluate the virucidal activity of "Bactercline acne". A certain quota of a viral suspension was added to "Bactercline acne" both in "clean state", i.e. in a water solution containing 0.3 g/1 of bovine albumin, and in "dirty state", i.e. in a water solution containing 3.0 g/1 of bovine albumin and 0.3 ml of erythrocytes.
Suspension containing Adenovirus type 5 (ATCC VR5) and Poliovirus 1 Sabin strain having a titre, evaluated as Logio of ID50, respectively of Adenovirus type 5 5-8.15 for
Adenovirus type 5 and 1-8.20 for Poliovirus 1 Sabin strain, and with different dilution ratio comprised between 0
(undiluted suspension) and 10~4, were prepared, such suspensions were brought into contact with layers of HeLa cells at about 90%, those cells had been cultivated in MEM with 2% FBC, to evaluate the maximum viral concentration that does not cause morphological mutation in the cells. Such a maximum concentration is 10"1. Therefore in tests undiluted suspensions of viruses have been used. The viral suspensions and "Bactercline acne" were kept in contact at a temperature of about 200C for preset time intervals: 1 min, 10 min, 30 min, 60 min.
After each one of said time intervals a certain quantity of the mixture containing the viral suspension and "Bactercline acne" was removed, diluted using a 1:10 dilution ratio with a Minimal Essential Medium (MEM) and 2% of Fetal Calf Serum (FCS) to block the virucidal activity, and then analyzed for evaluating the virucidal activity.
The virucidal activity was evaluated calculating the ID50 i.e. the dilution of the viral suspension that causes cytopathic effects in 50% of the samples, as according to the "Spearman-Karber method".
The results of the tests are shown in the following table 7 and table 8 respectively for suspension of Poliovirus and Adenovirus 5.
Figure imgf000049_0001
Table 7
Figure imgf000049_0002
Table 8
The values in second and third column of the aforementioned tables 7, 8, indicate the negative logarithm of the 50% of the end-point.
The results obtained, show that a reduction higher than 4Logio of the viral titre of the suspensions contacted with "Bactercline acne" has been obtained for both the viral suspensions either in "clean" and in "dirty" state samples; the samples had contact time interval of about 10 min.
Therefore a high virucidal activity of "Bactercline acne" has been demonstrated.
The methodology of such tests has been verified for validating the results obtained. Such a validation has obtained positive results.
Example 10 Method for producing a topical-treatment product containing the composition having the general formula AOx- (L-
Using the composition having the general formula AOx- (L-Men+) x many different kind of topical-treatment products may be obtained, since the composition having the general formula AOx- (L-Men+) ! may be suitably mixed with many different substances .
For example a product to be used for treating ulcers, and in particular bedsores, or decubitus ulcers, may be obtained. In the following table 9 the percentage contents of a cream for topical use for treating ulcers are indicated.
Figure imgf000050_0001
Table 9
The aforementioned compounds are weighed and dosed.
A turboemulsifier is heated up to a temperature of about 65°-
700C.
Phase "A": The compounds having the value "A" in the fourth column of the above table 2 are introduced into a turboemulsifier and mixed together. The turboemulsifier is heated up to a temperature of about 65°-70°C, so that the compounds in the turboemulsifier melt, and in the mean time the compounds are mixed. Complete melting of the compounds has to be achieved, so that a better mixing can be obtained.
Phase "B": A further turboemulsifier is heated up to a temperature of about 75°-80°C. The compounds having the value "B" in the fourth column of the above table 2 are introduced in the further turboemulsifier, mixed together.
As the compounds in the turboemulsifier and in the further turboemulsifier reach the respective desired temperature values, both the turboemulsifier and the further turboemulsifier are closed, and operated so that the respective compounds in the turboemulsifier and in the further turboemulsifier could be mixed and homogenized. Therefore, a vacuum pump, connected to the turboemulsifier is operated, and the compounds in the further turboemulsifier are poured into the turboemulsifier, i.e. compounds of phase "B" are poured in the compounds of phase "A".
The turboemulsifier is operated for few minutes so that the compounds of phase "A" and of phase "B" mix and homogenize together, the real mixing of the mixture can be checked and, if necessary, the turboemulsifier may be operated again. After a desired mixing of the mixture has been obtained, the vacuum pump is operated, and the turboemulsifier is cooled down to a temperature of about 45°C-50°C.
After such a temperature value has been reached, the vacuum pump is switched off and the compounds having the value "C" in the fourth column of the above table 9 are introduced into the turboemulsifier .
The turboemulsifier and the vacuum pump are both operated so that the compounds can be mixed and homogenized together, and the turboemulsifier is cooled during the homogenizing, down to a temperature of about 20°-30°C.
Such a temperature value is maintained for a certain time interval during which the compounds are continuously mixed. After a certain time interval the product may be poured out form the turboemulsifier and analyzed. Analysis carried out have been demonstrated that the product is very stable over time and can be packed in subsequent packing operations and stocked without any risk of separations of the single compounds of the product.
The product obtained, called "Bactercline ulcer" hereinbelow for the sake of brevity, is an emulsion containing the composition having the general formula AOx- (L-Men+) x and additives, and other active principles, that can be used for obtaining topical-treatment products.
"Bactercline ulcer" is in a form of a cream that can be used for treating many skin ulcers, and in particular decubitus ulcers . Owing to the very limited dimension of the composition having the general formula AOx- (L-Men+) ± and the features thereof, an emulsion having very homogenous features is obtained. As the compound having the general formula AOx- (L-Men+) ± may for example used a compound containing titanium dioxide (TiO2) as AOx, silver perchlorate (Ag+ClO4 ") as Men+ and a bifunctional ligand L suitable for bond both the titanium dioxide and the silver perchlorate.
Preferably 2 g of the compound having the general formula AOx- (L-Me11"1") ! contain 1.998g of TiO2, 0.0084g of AgClO4, and 0.0062g of of 4-mercaptophenyl boronic acid as bifunctional ligand L.
A quaternary ammonium salt is also present, i.e. benzalkonium chloride that enhance the antibacterial, antimycotic, antimicrobial, antiviral properties of "Bactercline ulcer". Similar "Bactercline ulcer" preparations may also be obtained using as bifunctional ligand L 6-mercaptonicotinic acid, and/or 11-mercaptoundecanoic acid, and/or mercaptosuccinic acid. The "Bactercline ulcer" is a creamy, odourless emulsion, a water-in-oil-in water emulsion, having a white colour, with a density of about 0.995-1.005 g/cm3 , and a viscosity of about 50,000-60,000 centipoise The creamy emulsion obtained may be spread on the skin, preferably twice a day, owing to the physical features thereof the cream may be spread very easily, and forms on the skin of a user a protective layer, that is invisible and thus not unsightly, and that disinfect the skin allowing the ulcers to be treated.
The cutaneous tolerance of "Bactercline ulcer" has been tested on 50 adult volunteers, applying a 48-hours "Single patch test" under dermatological control. The volunteers comprises 45 women and 5 men, aged between 18 and 65 years, average age 40 years, have normal skin and correspond to inclusion and non-inclusion criteria defined by DERMASCAN Group. Inclusion criteria specified that the volunteers had given their informed written consent, had no previous experience of intolerance or allergic reactions to cosmetic products, belonged to phototype I to III.
Non inclusion criteria specified that the persons having the following features are not included as volunteers in the study: pregnant or nursing women, or women planning to be pregnant during the study, persons having cutaneous pathology
(eczema, psoriasis, vitiligo, pytiriasis versicolor, acne,...) on the zone of the experiment; volunteers currently taking or who stopped taking: antibiotics, anti-histamines, systemic anti-inflammatory drugs, or corticoids during the previous week, cough-suppressants or corticoids during the previous four weeks, retinoids, immunosuppressive drugs, anti-cancer drugs during the previous six months; volunteers who started, stopped, or changed hormonal treatment, including contraceptive pills, in the previous five week; volunteers whose skin has been exposed to the sun or to UV rays during the previous month; volunteers with very sensitive skin; volunteers having significant hair on the back, freckles, beauty spots, or a tattoo on the back; volunteers with serious diseases, volunteers using excessive quantity of alcohol or tobacco. The product was applied on the scapular part of the back, using patch test of the type "Finn Chambers ®" 8mm (50mm2) of the occlusive type, using a dose of product for each patch test of 25μl of the product in pure state.
Each patch was maintained on the skin of the volunteers for
48 hours.
Control patches without the product to be tested have been also applied to the volunteers.
After the 48-hours time interval the patches were removed from the skin, and after 30 min from the removal, a macroscopic skin examination was conducted with daylight lamps to evaluate the irritation grade of each one of the zones of the skin that had received the product.
Such evaluation was conducted comparing the real irritation of the skin with that obtained with the negative control patches .
If there was no local skin reaction at the 30 minutes reading after patch removal, the study was finished.
Nevertheless each volunteers was asked to confirm that there was non visible reactions the day after. If the volunteer had a visible reaction, he had to return and readings were taken until reversibility of the cutaneous reactions.
The scale in the following table 10 has been used to evaluate the degree of irritation:
Criteria description
Score Quotation
Erythema "E' Oedema "O"
Absent Normal aspect, no erythema Normal aspect, no oedema barely perceptible: slight
0.5 Doubtful pink coloration of one partPalpable, barely visible of the tested area slight pink coloration of the omplete tested area, or
Slight Palpable, visible rather visible on one part of the tested area
Obvious oedema with o:
Obvious erythema covering the
Obvious without papule (s) o: whole tested area vesicle (s)
Severe erythema covering allSevere oedema (diffusing the tested area or erythemaoutside the tested area)
Important diffusing outside the testedwith or without papule (s) area or vesicle (s
Table 10 A change in the skin structure, for example dryness (D) , roughness (Rl), thickness (T), reflectivity (R2), that could be linked to the nature of the product or one of its components was subjected to a clinical description and its intensity was graded according the following scale: 0.5=doubtful, l=slight, 2=obvious, 3=important. The analysis and the interpretation were carried out according to the results obtained in the experimental conditions at each reading. The cutaneous tolerance of the cream has been evaluated calculating the "Mean Irritation Index" (Mil) at each reading according to the formula MII=(E total cutaneous reactions score/ (Total number of volunteers) , a cutaneous reaction may be erythema and/or oedema, in case of presence of both erythema and oedema, the score of both erythema and oedema reactions were added.
The index Mil obtained was used for arbitrarily classifying the product under study according to the following scale in table 11:
M.I.I. Class
M.I.I.<0.20 non-irritating (NI)
0.20<M.I.I. <0.50 slightly-irritating (SI)
0.50<M.I.I. <1 moderately irritating (MI)
M.I.I.≥l Irritating (I)
Table 11
M.I.I, was calculated for "Bactercline ulcer" either 30 min after the spreading of "Bactercline ulcer" on the skin of the volunteers, and 24-hours after the spreading. Both the tests show a M.I.I, value for "Bactercline ulcer" of 0.00, therefore the cream produced is a non-irritating product .
Similar considerations may apply to "Bactercline acne" since the composition of the two products "Bactercline ulcer" and "Bactercline acne" is very similar, and also "Bactercline ulcer" contain more potentially aggressive compounds, therefore since "Bactercline ulcer" does not cause any irritation in the tested person, even more "Bactercline acne" would not have any irritation effect. Under test conditions, it can be concluded that the product obtained according to the example 8 and tested under dermatological control and applied pure and locally under occlusive patch for 48 hours, to the skin of 50 adult volunteers, is classified as non-irritating at the 30 minute and 24-hours readings, according to the calculation of M.I.I. The study has been carried out from 17/07/06 to 20/07/06 and from 24/07/06 to 27/07/06 by the clinical Unit PROCOS, Warsaw, Poland. The study was conducted according to the Good clinical Practice Guidelines from FDA (FR of 08/08/1978 Part V - Decree Nr. 77N-0278), EEC (Directives Nr. 91/507 and III 3976/88 of 11/07/1990) and to the ministry of health of the French Republic. The study was conducted according to Standard Operating Procedures and the Protocol defined by the sponsor. All the test events recorded during the study were reported. Controls on data veracity and conformity to the protocol were conducted and confirmed by persons participating in the study.
Tests have been conducted according the standard procedure described in "European Standard EN14476, May 2002 (phase 2 ; step 1) edited by European Committee for standardization to evaluate the virucidal activity of "Bactercline ulcer". A certain quota of a viral suspension is added to "Bactercline ulcer" both in "clean state", i.e. in a water solution containing 0.3 g/1 of bovine albumin, and in "dirty state", i.e. in a water solution containing 3.0 g/1 of bovine albumin and 0.3 ml of erythrocytes. Suspension containing Adenovirus type 5 (ATCC VR5) and Poliovirus 1 Sabin strain having a titre, evaluated as Logio of ID50, respectively of 5 5-8.15 for Adenovirus type 5 and of 1-8.20 for Poliovirus 1 Sabin strain and with different dilution rate comprised between 0 (undiluted suspension) and 10~4, were prepared, such suspensions were brought into contact with layers of HeLa cells at about 90%, these cells had been cultivated in MEM with 2% FBC, to evaluate the maximum viral concentration that does not cause morphological mutation in the cells.
Such a maximum concentration is 10"1. Therefore in tests undiluted suspensions of viruses have been used. The viral suspensions and "Bactercline ulcer" were kept in contact at a temperature of about 200C for preset time intervals: 1 min, 10 min, 30 min, 60 min.
After each one of said time intervals a certain quantity of the mixing containing the viral suspension and "Bactercline ulcer" was removed, diluted using a 1:10 dilution ratio with a Minimal Essential Medium (MEM) and 2% of Fetal Calf Serum
(FCS) for blocking the virucidal activity, and then analyzed to evaluate the virucidal activity of "Bactercline ulcer".
The virucidal activity was evaluated calculating the ID50, i.e. the dilution of the viral suspension that causes cytopathic effects in 50% of the samples, as according to the
"Spearman-Karber method".
The results of the tests are shown in the following table 12 and table 13, respectively for suspension of Poliovirus and Adenovirus 5.
Figure imgf000057_0001
Table 12
Figure imgf000057_0002
Table 13
The values in second and third columns of the aforementioned tables 12, 13, indicate the negative logarithm of the 50% of the end-point. The results obtained, show that a reduction higher than
4Logio of the viral titre of the suspensions contacted with "Bactercline ulcer" was obtained for both the viral suspensions both in "clean" and in "dirty" states, for samples having a contact time interval of about 10 min.
The high virucidal activity of "Bactercline acne" was thus demonstrated.
The methodology of such tests has been verified for validating the results obtained. This validation was positive.

Claims

1. Use of a composition with the general formula AOx-(L- Men+)i for obtaining a topical-treatment product for treating acne diseases.
2. Use of a composition having the general formula AOx-(L- Men+)i for a obtaining topical-treatment product for treating herpes diseases.
3. Use of a composition having the general formula AOx-(L- Men+)i for a obtaining topical-treatment product for treating skin ulcers, in particular decubitus ulcers.
4. Use of composition a having the general formula AOx-(L- Men+)i for obtaining a topical-treatment product for treating skin irritations, and/or skin inflammations, and/or skin abrasions, and/or skin excoriations.
5. Use of a composition having the general formula AOx-(L- Men+)i for obtaining a lenitive topical-treatment product .
6. Use of a composition having the general formula AOx-(L- Men+)i for obtaining a cicatrizing topical-treatment product for cicatrizing the skin of a user of said cicatrizing product.
7. Use of a composition having the general formula AOx-(L- Men+)i for obtaining a burn topical-treatment product for treating burns on the skin of a user of said topical-treatment product.
8. Use of a composition having the general formula AOx-(L- Men+)i for obtaining a deodorizing topical-treatment product .
9. Use of a composition having the general formula AOx-(L- Men+)i for obtaining a skincare topical-treatment product having antiviral, and/or antibacterial, and/or antimicrobial, and/or antimycotic properties.
10. Use according to claim 9, wherein said skincare topical-treatment product comprises day cream means, and/or night cream means, and/or cleansing cream means, and/or cleansing gel means, and/or moisturizing cream means, and/or anti-wrinkle cream means, and/or solar cream means .
11. Use according to any one of claims 1 to 10, wherein said topical-treatment product comprises at least a compound having antiviral, and/or antibacterial, and/or antimicrobial, and/or antimycotic properties.
12. Use according to any one of claims 1 to 11, wherein said topical-treatment product comprises at least a compound effective in treating at least one of the following microbes: HSV-I (Herpes Simplex Virus-1) , Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherica CoIi, Salmonella enteridis Dl, Listeria monocytogenes, Candida albicans, Aspergillus niger.
13. Use according to any one of the claims 1 to 12, wherein said composition having the general formula AOx- (L-Men+) x further comprises at least quaternary ammonium salt for enhancing the properties of said topical-treatment product .
14. Use according to claim 13, wherein said composition having the general formula AOx- (L-Men+) ± further comprises at least a chloride ammonium salt, such as benzalkonium chloride.
15. Use according to any one of claims 1 to 14, wherein said topical-treatment product comprises a cream product, and/or a gel product, and/or a powder product, and/or an emulsion product, and/or a suspension product, and/or a microspheres product, and/or a granular product, and/or a multiple emulsion product, and/or a water-in-oil-in water emulsion product.
16. Use according to any one of claims 1 to 15, wherein said composition comprises at least an antibacterial component .
17. Use according to any one of claims 1 to 16, wherein said composition further comprises at least an antiviral component.
18. Use according to any one of claims 1 to 17, wherein said composition further comprises at least a antimycotic component.
19. Use according to any one of claims 1 to 18, wherein said composition further comprises at least an antimicrobial component.
20. Use according to any one of claims 1 to 19, wherein said composition further comprises at least a photocatalytic component.
21. Use according to any one of claims 1 to 20, wherein said composition further comprises at least an antipollution component.
22. Use according to any one of claims 1 to 21, wherein Men+ is a metal having antibacterial, and/or antimicrobial, and/or antimycotic, and/or antiviral properties.
23. Use according to any one of claims 1 to 22, wherein Men+ is selected in a group comprising Ag+ and Cu++ .
24. Use according to any one of claims 1 to 23, wherein AO is an oxide provided with antibacterial and/or antimicrobial, and/or antimycotic, and/or antiviral, and/or photocatalytic, and/or anti-pollution properties .
25. Use according to any one of claims 1 to 24, wherein AOx is an oxide selected in a group comprising colloidal silica, titanium dioxide, zirconium dioxide, stannic dioxide, and zinc oxide.
26. Use according to any one of claims 1 to 25, wherein AOx comprises titanium dioxide, with Titanium substantially in Anatase form.
27. Use according to any one of claims 1 to 26, and further comprising a cationic surfactant bonded to said ligand
L.
28. Use according to claim 27, wherein said cationic surfactant is chosen in a group comprising alkylammonium salts, preferably quaternary ammonium compounds, benzyl C12-C14, Ci-alkylammonium chloride, benzalkonium chloride.
29. Use according to any one of claims 1 to 28, wherein L is a molecule comprising at least a first functional group bonded to said metal oxide AOx, and at least a second functional group bonded to said ion Me+.
30. Use according to claim 29, wherein said first functional group comprises boronic (-B(OH)2), and/or phosphonic (-PO3H2) , and/or carboxyl (-COOH) functionality.
31. Use according to claim 29, or 30, wherein said second functional group can be selected in a group comprising
Cl", Br", I", S, CNS", =N, -NH2, CN", and NCS".
32. Use according to any one of claims 1 to 31, wherein said ligand L is selected in a group comprising nitrogen-containing heterocycles having 6 to 18 members .
33. Use according to claim 32, wherein at least one of said nitrogen-containing heterocycles is substituted with one or more substituents selected in a group comprising from: carboxyl (-COOH) , boronic (-B(OH)2), phosphonic (- POsH2) , mercaptan (-SH), and hydroxyl (-OH) group.
34. Use according to any one of claims 1 to 33, wherein said ligand L is selected in a group comprising Ce to C18 aryls.
35. Use according to claim 34, wherein at least one of said C6 to C18 aryl is selected in a group comprising: phenyl, naphthyl, and biphenyl .
36. Use according to claim 34, or 35, wherein at least one of said aryl is substituted with one or more substituent chosen from a group comprising carboxyl (- COOH), boronic (-B(OH)2), phosphonic (-PO3H2), mercaptan (-SH), and hydroxyl (-0H).
37. Use according to any one of claims 1 to 36, wherein said ligand L can be chosen in a group comprising C2 to C18 carboxylic acid, preferably monocarboxylic and dicarboxylic acids.
38. Use according to claim 37, wherein at least one of said carboxylic acid is substituted with one or more mercaptan groups (-SH) and/or hydroxyl groups (-0H) .
39. Use according to any one of claims 1 to 38, wherein said ligand L is selected from a group comprising: pyridine, dipyridyl, and terpyridyl, functionalized with carboxyl groups, boronic groups, or phosphonic groups; mercaptosuccinic acid, mercaptoundecanoic acid, mercaptophenol, 6-mercaptonicotinic acid, 5- carboxypentanethiol, mercaptobutyric acid, and 4- mercaptophenylboronic acid.
40. Use according to any one of claims 1 to 39, wherein said first functional group and said second functional group are coordinated at metal atom (M) of said ligand L.
41. Use according to claim 40, wherein said metal atom (M) can be chosen between any metals in the first, second, or third row of transition metals in the periodic table of the elements.
42. Use according to claim 40, or 741, wherein said metal atom can be chosen in a group comprising: Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Re, Os, Ir, Pt.
43. Use according to any one of claims 1 to 43, wherein said ligand L comprises dipyridyl, and/or terpyridyl molecule to which said first functional group is bonded.
44. Use according to claim 43, wherein at least one of said dipyridyl and/or terpyridyl molecule is substituted with carboxyl groups.
45. Use according to claim 43, or 44, wherein at least one of said dipyridyl and/or terpyridyl molecule is substituted with carboxyl groups in the para position with respect to the pyridine nitrogen.
46. Use according to any one of claim 1 to 45, wherein said ligand L has a geometric structure chosen in group comprising octahedral, tetrahedral, rectangular planar or square planar, bipyramidal trigonal, or pyramidal with a square or rectangular base.
47. Use according to any one of claim 1 to 46, wherein said composition comprises [ (H3Tcterpy) M (CN) 3] TBA, in which H3Tcterpy is 4, 4' , 4"-tricarboxy terpyridyl, TBA is tetrabutylammonium cation, M is a metal atom a which first functional group and second functional group of said ligand L are coordinated.
48. Use according to any one of claim 1 to 47, wherein said composition comprises [ (H3Tcterpy) M (NCS) 3] TBA, in which
H3Tcterpy is 4, 4' , 4"-tricarboxy terpyridyl, TBA is tetrabutylammonium cation, M is a metal atom a which first functional group and second functional group of said ligand L are coordinated.
49. Use according to any one of claim 1 to 478, wherein said composition comprises [M (H3Tcterpy) (bpy) NCS] TBA, in which H3Tcterpy is 4, 4' , 4"-tricarboxy terpyridyl, bpy is 2, 2' -dipyridyl, TBA is tetrabutylammonium cation, M is a metal atom a which first functional group and second functional group of said ligand L are coordinated.
50. Use according to any one of claim 1 to 49, wherein said composition comprises M (H2dcb) 2 (NCS) 2, in which H2dcb is 2 , 2 ' -dipyridyl-4 , 4 ' -dicarboxylic acid, M is a metal atom a which first functional group and second functional group of said ligand L are coordinated.
51. Use according to any one of claims 1 to 50, wherein said composition has particle size less than 40 nm, preferably less than 30 nm.
52. Use according to any one of claims 1 to 51, wherein said composition has particle size less than 15 nm.
53. Use according to any one of claims 1 to 52, wherein said composition comprises at least a component for killing at least a microorganism chosen in a group comprising: HSV-I (Herpes Simplex Virus-1) , Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila , Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherica CoIi, Salmonella enteridis Dl, Listeria monocytogenes, Candida albicans, Aspergillus niger, Pseudomonas, Erwinia amilovora , Xanthomonas campestris .
54. Use according to any one of claims 1 to 53, wherein said topical-treatment product further comprises additives, and/or active principle, and/or excipients, and/or suitable for obtaining a dermatological product.
55. Use according to any one of claims 1 to 53, wherein said topical-treatment product further comprises glycerin, and/or amidopropylene glycol, and/or magnesium silicate, and/or aluminum silicate and/or vaseline, and/or liquid paraffin, and/or stearyl alcohol, and/or polyethylene glycol stearate, and/or carboxypolymethylene, and/or sodium edetate.
56. Use of a topical-treatment product containing water, isopropyl palmitate, Petrolatum, Isohexadecane, Benzalkonium chloride 50%, Bees wax, PPG-15 stearylether, PEG-30 dipolyhydroxystearate, Methylparaben, Propylparaben, Citric acid, Sodium dehydroacetate, Magnesium sulphate, 2,4 Bromonitropropandiol and a composition having general AOx-(L-Me1^)1, in which AOx is TiO2, Men+ is AgClO4 " and L is a ligand suitable to bond both the TiO2 and AgClO4- for treating ulcers, such as decubitus ulcers.
57. Use of a topical-treatment product containing water, PPG-15-sterarylether, Steareth-2, Cetearyl alcohol, Benzalkonium chloride, Steareth-21, Dimethicone, Methylparaben, Propylparaben, Citric acid, Sodium dehydroacetate, Butylated Hydroxyanisole (BHA) , Butylated Hydroxytoluene (BHT), 2,4 Bromonitropropandiol and a composition having general AOx-(L-Me^)1, in which AOx is TiO2, Men+ is AgClO4 " and L is a ligand suitable to bond both the TiO2 and AgClO4 ", for treating acne diseases.
58. Use of a topical-treatment product containing water, PPG-15-sterarylether, Steareth-2, Cetearyl alcohol, Benzalkonium chloride, Steareth-21, Dimethicone, Methylparaben, Propylparaben, Citric acid, Sodium dehydroacetate, Butylated Hydroxyanisole (BHA) , Butylated Hydroxytoluene (BHT), 2,4 Bromonitropropandiol and a composition having general AOx-(L-Me1^)1, in which AOx is TiO2, Men+ is AgClO4 " and L is a ligand suitable to bond both the TiO2 and AgClO4-, for treating herpes diseases.
59. Use according to any one of claims 56 to 58, wherein said ligand L is chosen in a group comprising: 4- mercaptophenyl boronic acid, 6-mercaptonicotinic acid, 11-mercaptoundecanoic acid, mercaptosuccinic acid.
60. Deodorizing product comprising a composition having the general formula AOx- (L-Men+) lr wherein
— AOx is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (0) bonded to the metal (A) atom,
— Men+ is a metal ion,
— L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AOx) and the metal ion (Men+) , and i is the number of (L-Men+) groups bound to the metal oxide AOx; the value of the parameter i depending on various factors, such as the size of the nanoparticle of AOx, the nature of the, molecule L.
61. Coating product comprising a composition having the general formula AOx- (L-Men+) lr wherein
— AOx is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (0) bonded to the metal (A) atom,
— Men+ is a metal ion, — L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AOx) and the metal ion (Men+) , and i is the number of (L-Men+) groups bound to the metal oxide AOx; the value of the parameter i depending on various factors, such as the size of the nanoparticle of AOx, the nature of the, molecule L.
62. Coating product according to claim 61, and further comprising substrate means on which said composition is applied.
63. Coating product according to claim 61, or 62, wherein said substrate is chosen in a group comprising tile means, panel means, textile means, leather coating means, furniture means, plastic, cement, linoleum, glass, wood, ceramic, composite material, fabric, natural rubber, synthetic rubber, natural stones, marble, metal, alloy, aluminium, iron, textiles, carpeting, rugs.
64. Coating product according to any one of claims 61 to 63, wherein said product comprises a painting product.
65. Coating product according to any one of claims 61 to 64, said product comprises a transparent painting product .
66. Coating product according to claim 64, or 65, and further comprising pigment means.
67. Coating product according to any one of claims 64 to 66 and further comprising binder means chosen in a group comprising: synthetic resins, natural resins, acrylics, polyurethanes, polyesters, melamines, epoxy, oils.
68. Coating product according to any one of claims 64 to 67, and further comprising filler means chosen in a group comprising: talc, clay, lime, baryte .
69. Coating product according to any one of claims 64 to 68 and further comprising diluent means, chosen in a group comprising: organic solvents, petroleum distillate, alcohols, ketones, esters, glycol ethers, water, synthetic resins, synthetic resins having low molecular weight .
70. Coating product according to any one of claims 64 to 69 and further comprising additive means chosen in a group comprising: pigments, dyes, catalysts, thickeners, stabilizers, emulsifiers, texturizers, adhesion promoting means, flatteners.
71. Coating product according to any one of claims 64 to 70, wherein said painting product is chosen in a group comprising: varnish, lacquer, latex paint, enamel, fingerpaint, ink, anti-graphiti paint, anti-climb paint, lacquer, fresco paint.
72. Product comprising a base material and a composition having the general formula AOx- (L-Men+) lr wherein
— AOx is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (0) bonded to the metal (A) atom,
— Men+ is a metal ion,
— L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AOx) and the metal ion (Men+) , and i is the number of (L-Men+) groups bound to the metal oxide AOx; the value of the parameter i depending on various factors, such as the size of the nanoparticle of AOx, the nature of the, molecule L.
73. Product according to claim 72, wherein said composition is mixed to said base material in a flowable state.
74. Product according to claim 72, or 73, wherein said composition is mixed to said base material in a melt state .
75. Product according to any one of claims 72 to 74, wherein said base material is chosen in a group comprising: plastic, glass, wood, ceramic material, composite material, textile, fabric, natural rubber, synthetic rubber, natural stones, marble, metal, alloy, leather, footwear material.
76. Cleansing product comprising a composition having the general formula AOx- (L-Men+) lr wherein
— AOx is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (0) bonded to the metal (A) atom,
— Men+ is a metal ion, — L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AOx) and the metal ion (Men+) , and i is the number of (L-Men+) groups bound to the metal oxide AOx; the value of the parameter i depending on various factors, such as the size of the nanoparticle of AOx, the nature of the, molecule L
77. Cleansing product according to claim 76, wherein said composition comprises at least a component efficacious at least against organism chosen in a group comprising: HSV-I (Herpes Simplex Virus-1) , Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherica CoIi, Salmonella enteridis Dl, Listeria monocytogenes, Candida albicans, Aspergillus niger.
78. Cleansing product according to claim 76, or 77, wherein said cleansing product is chosen in a group comprising: floor detergent, skin detergent, shamopoo, dish- detergent, cloth-detergent, glass detergent, hand soap, hair-conditioner .
79. Cleansing product according to any one of claims 76 to
78, and further comprising surfactant means.
80. Cleansing product according to any one of claims 76 to
79, and further comprising abrasive means.
81. Cleansing product according to any one of claims 76 to
80, and further comprising pH modifying means.
82. Cleansing product according to claim 81, wherein said pH modifying means comprises acids and/or caustics.
83. Cleansing product according to any one of claims 76 to
82, and further comprising water softeners.
84. Cleansing product according to any one of claims 76 to
83, and further comprising oxidants.
85. Cleansing product according to any one of claims 76 to
84, and further comprising non-surfactants materials.
86. Cleansing product according to any one of claims 76 to
85, and further comprising enzymes.
87. Cleansing product according to any one of claims 76 to 86, and further comprising foaming modifying means.
88. Cleansing product according to any one of claims 76 to 87, and further comprising optical brighteners, and/or softeners, and/or colours, and/or perfumes, and/or essences .
89. Cleansing product according to any one of claims 76 to
88, and further comprising sodium laureth sulfate.
90. Cleansing product according to any one of claims 76 to
89, and further comprising glycol distearate.
91. Cleansing product according to any one of claims 76 to
90, and further comprising natural oil means, such as for example coconut oil, linseed oil, and/or tocopherol, and/or Pantothenic acid.
92. Sterilising product comprising a cleansing product according to any one of claims 76 to 91.
93. Sterilising product comprising a composition having the general formula AOx- (L-Men+) lr wherein — AOx is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (O) bonded to the metal (A) atom,
— Men+ is a metal ion,
— L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AOx) and the metal ion (Men+) , and i is the number of (L-Men+) groups bound to the metal oxide AOx; the value of the parameter i depending on various factors, such as the size of the nanoparticle of AOx, the nature of the, molecule L.
94. Sterilising product according to claim 92, or 93 and further comprising at least a component efficacious at least against an organism chosen in a group comprising: HSV-I (Herpes Simplex Virus-1) , Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila , Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherica CoIi, Salmonella enteridis Dl,
Listeria monocytogenes, Candida albicans, Aspergillus niger.
95. Biocide product comprising a composition having the general formula AOx- (L-Men+) lr wherein — AOx is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (0) bonded to the metal (A) atom,
— Men+ is a metal ion, — L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AOx) and the metal ion (Men+) , and i is the number of (L-Men+) groups bound to the metal oxide AOx; the value of the parameter i depending on various factors, such as the size of the nanoparticle of AOx, the nature of the, molecule L.
96. Biocide product according to claim 95, wherein said product is chosen in a group comprising: pesticides, antimycotics, herbicides, insecticides, algicides, moluscicides, miticides, insecticides, rodenticides, antimicrobial products, germicides, antibiotics, antibacterials, antivirals, antifungals, antiprotoas, antiparasites, preservatives.
97. Biocide product according to claim 95, or 96, wherein said product comprises at least a component efficacious at least against organism chosen in a group comprising: Pseudomonas, Erwinia amilovora , Xanthomonas campestris .
98. Biocide product according to any one of claims 95 to 98, wherein said product comprises an organophosphate pesticide, and/or a carbamate pesticide.
99. Prosthesis product comprising a composition having the general formula AOx- (L-Men+) lr wherein
— AOx is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (0) bonded to the metal (A) atom, — Men+ is a metal ion,
— L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AOx) and the metal ion (Men+) , and i is the number of (L-Men+) groups bound to the metal oxide AOx; the value of the parameter i depending on various factors, such as the size of the nanoparticle of AOx, the nature of the molecule L.
100. Prosthesis product according to claim 99, wherein said composition is mixed to a prosthesis material of said prosthesis product.
101. Prosthesis product according to claim 99, or 100, wherein said prosthesis product is chosen in a group comprising dental prosthesis, osseous-prosthesis.
102. Sanitary napkin product comprising a composition having the general formula AOx- (L-Men+) lr wherein
— AOx is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (O) bonded to the metal (A) atom,
— Men+ is a metal ion,
— L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AOx) and the metal ion (Men+) , and i is the number of (L-Men+) groups bound to the metal oxide AOx; the value of the parameter i depending on various factors, such as the size of the nanoparticle of AOx, the nature of the molecule L.
103. Sanitary napkin product according to claim 102, wherein said composition is mixed to absorbent material means of said sanitary napkin product.
104. Sanitary napkin product according to claim 102, or 103, wherein said composition is applied to surface means of said sanitary napkin product intended to go in use in contact with the skin of an user of said sanitary napkin product.
105. Sanitary napkin product according to any one of claims 102 to 104, wherein said composition is applied to further surface means of said sanitary napkin product arranged opposite to surface means intended to go in use in contact with the skin of an user of said sanitary napkin product.
106. Product according to any one of claims 1 to 105, wherein said composition comprises at least an antibacterial component.
107. Product according to any one of claims 1 to 106, wherein said composition further comprises at least an antiviral component.
108. Product according to any one of claims 1 to 107, wherein said composition further comprises at least a antimycotic component.
109. Product according to any one of claims 1 to 108, wherein said composition further comprises at least an antimicrobial component.
110. Product according to any one of claims 1 to 109, wherein said composition further comprises at least a photocatalytic component.
111. Product according to any one of claims 1 to 110, wherein said composition further comprises at least an antipollution component.
112. Product according to any one of claims 1 to 111, wherein Men+ is a metal having antibacterial, and/or antimicrobial, and/or antimycotic, and/or antiviral properties .
113. Product according to any one of claims 1 to 112, wherein Men+ is selected in a group comprising Ag+ and Cu .
114. Product according to any one of claims 1 to 113, wherein AOx is an oxide provided with antibacterial and/or antimicrobial, and/or antimycotic, and/or antiviral, and/or photocatalytic, and/or anti-pollution properties .
115. Product according to any one of claims 1 to 114, wherein AOx is an oxide selected in a group comprising colloidal silica, titanium dioxide, zirconium dioxide, stannic dioxide, and zinc oxide.
116. Product according to any one of claims 1 to 115, wherein AOx comprises titanium dioxide, with Titanium substantially in Anatase form.
117. Product according to any one of claims 1 to 116, and further comprising a cationic surfactant bonded to said ligand L.
118. Product according to claim 117, wherein said cationic surfactant is chosen in a group comprising alkylammonium salts, preferably quaternary ammonium compounds, benzyl C12-C14, Ci-alkylammonium chloride, benzalkonium chloride.
119. Product according to any one of claims 1 to 118, wherein L is a molecule comprising at least a first functional group bonded to said metal oxide AOx, and at least a second functional group bonded to said ion Me+.
120. Product according to claim 119, wherein said first functional group comprises boronic (-B(OH) 2) , and/or phosphonic (-PO3H2) , and/or carboxyl (-COOH) functionality.
121. Product according to claim 119, or 120, wherein said second functional group can be selected in a group comprising Cl", Br", I", S, CNS", =N, -NH2, CN", and NCS".
122. Product according to any one of claims 1 to 121, wherein said ligand L is selected in a group comprising nitrogen-containing heterocycles having 6 to 18 members .
123. Product according to claim 122, wherein at least one of said nitrogen-containing heterocycles is substituted with one or more substituents selected in a group comprising from: carboxyl (-COOH) , boronic (-B(OH)2), phosphonic (-POsH2), mercaptan (-SH), and hydroxyl (-0H) group .
124. Product according to any one of claims 1 to 123, wherein said ligand L is selected in a group comprising C6 to C18 aryls.
125. Product according to claim 124, wherein at least one of said C6 to C18 aryl is selected in a group comprising: phenyl, naphthyl, and biphenyl .
126. Product according to claim 124, or 125, wherein at least one of said aryl is substituted with one or more substituent chosen from a group comprising carboxyl (-
COOH), boronic (-B(OH)2), phosphonic (-POsH2), mercaptan
(-SH), and hydroxyl (-0H).
127. Product according to any one of claims 1 to 126, wherein said ligand L can be chosen in a group comprising C2 to Cis carboxylic acid, preferably monocarboxylic and dicarboxylic acids.
128. Product according to claim 127, wherein at least one of said carboxylic acid is substituted with one or more mercaptan groups (-SH) and/or hydroxyl groups (-0H) .
129. Product according to any one of claims 1 to 128, wherein said ligand L is selected from a group comprising: pyridine, dipyridyl, and terpyridyl, functionalized with carboxyl groups, boronic groups, or phosphonic groups; mercaptosuccinic acid, mercaptoundecanoic acid, mercaptophenol, 6- mercaptonicotinic acid, 5-carboxypentanethiol, mercaptobutyric acid, and 4-mercaptophenylboronic acid.
130. Product according to any one of claims 119 to 121, or according to claim 122, or 123 if claim 122 is appended to any one of claims 119 to 121, or according to any one of claims 124 to 126 if claim 124 is appended to any one of claims 119 to 121, or to claim 122, or 123 if claim 122 is appended to any one of claims 119 to
121, or according to claim 127, or 128, if claim 127 is appended to any one of claims 119 to 121, or to claim
122, or 123 if claim 122 is appended to any one of claims 119 to 121, or to any one of claims 124 to 126 if claim 124 is appended to any one of claims 119 to 121, or to claim 122, or 123 if claim 122 is appended to any one of claims 119 to 121, or according to claim 129 if appended to any one of claims 119 to 121, or to claim 122, or 123 if claim 122 is appended to any one of claims 119 to 121, or to any one of claims 124 to 126 if claim 124 is appended to any one of claims 119 to 121, or to claim 122, or 123 if claim 122 is appended to any one of claims 119 to 121, wherein said first functional group and said second functional group are coordinated at metal atom of said ligand L.
131. Product according to claim 130, wherein said metal atom can be chosen between any metals in the first, second, or third row of transition metals in the periodic table of the elements.
132. Product according to claim 130, or 131, wherein said metal atom can be chosen in a group comprising: Cr, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Re, Os, Ir, Pt.
133. Product according to any one of claims 119 to 121, or according to claim 122, or 123 if claim 122 is appended to any one of claims 119 to 121, or according to any one of claims 124 to 126 if claim 124 is appended to any one of claims 119 to 121, or to claim 122, or 123 if claim 122 is appended to any one of claims 119 to
121, or according to claim 127, or 128, if claim 127 is appended to any one of claims 119 to 121, or to claim
122, or 123 if claim 122 is appended to any one of claims 119 to 121, or to any one of claims 124 to 126 if claim 124 is appended to any one of claims 119 to 121, or to claim 122, or 123 if claim 122 is appended to any one of claims 119 to 121, or according to claim 129 if appended to any one of claims 119 to 121, or to claim 122, or 123 if claim 122 is appended to any one of claims 119 to 121, or to any one of claims 124 to 126 if claim 124 is appended to any one of claims 119 to 121, or to claim 122, or 123 if claim 122 is appended to any one of claims 119 to 121, or according to any one of claims 130 to 132, wherein said ligand L comprises dipyridyl, and/or terpyridyl molecule to which said first functional group is bonded.
134. Product according to claim 133, wherein at least one of said dipyridyl and/or terpyridyl molecule is substituted with carboxyl groups.
135. Product according to claim 133, or 134, wherein at least one of said dipyridyl and/or terpyridyl molecule is substituted with carboxyl groups in the para position with respect to the pyridine nitrogen.
136. Product according to any one of claim 1 to 135, wherein said ligand L has a geometric structure chosen in group comprising octahedral, tetrahedral, rectangular planar or square planar, bipyramidal trigonal, or pyramidal with a square or rectangular base.
137. Product according to any one of claim 1 to 136, wherein said composition comprises [ (H3Tcterpy) M (CN) 3] TBA, in which H3Tcterpy is 4, 4' , 4"-tricarboxy terpyridyl, TBA is tetrabutylammonium cation, M is a metal atom a which first functional group and second functional group of said ligand L are coordinated.
138. Product according to any one of claim 1 to 137, wherein said composition comprises [ (H3Tcterpy) M (NCS) 3] TBA, in which H3Tcterpy is 4, 4' , 4"-tricarboxy terpyridyl, TBA is tetrabutylammonium cation, M is a metal atom a which first functional group and second functional group of said ligand L are coordinated.
139. Product according to any one of claim 1 to 138, wherein said composition comprises [M (H3Tcterpy) (bpy) NCS] TBA, in which H3Tcterpy is 4, 4' , 4"-tricarboxy terpyridyl, bpy is 2 , 2 ' -dipyridyl , TBA is tetrabutylammonium cation, M is a metal atom a which first functional group and second functional group of said ligand L are coordinated.
140. Product according to any one of claim 1 to 139, wherein said composition comprises M (H2dcb) 2 (NCS) 2, in which
H2dcb is 2, 2 ' -dipyridyl-4, 4 ' -dicarboxylic acid, M is a metal atom a which first functional group and second functional group of said ligand L are coordinated.
141. Product according to any one of claims 1 to 140, wherein said composition has particle size less than 40 nm, preferably less than 30 nm.
142. Product according to any one of claims 1 to 141, wherein said composition has particle size less than 15 nm.
143. Product according to any one of claims 1 to 142, wherein said composition comprises at least a component for killing at least a microorganism chosen in a group comprising: HSV-I (Herpes Simplex Virus-1) , Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherica CoIi, Salmonella enteridis Dl, Listeria monocytogenes, Candida albicans, Aspergillus niger, Pseudomonas, Erwinia amilovora, Xanthomonas campestris .
144. Material provided with coating means comprising a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
145. Prosthesis means provided with coating means comprising a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
146. Surgical instrument provided with coating means comprising a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
147. Filter means provided with coating means comprising a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
148. Air-circulating system comprising filter means according claim 147.
149. Air-circulating system comprising conduit means into which air flows, moving means for moving said air in said conduit, wherein at least portion means of said conduit means contacting said air is coated with coating means comprising a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
150. Sanitary napkin means provided with coating means comprising a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
151. Linen means provided with coating means comprising a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
152. Use of a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143, for obtaining antibacterial, and/or antimicrobial, and/or antimycotic, and/or self-cleaning and/or anti- pollution coating means.
153. Use according to claim 152, wherein said coating means is chosen in a group comprising tile means, panel means, linoleum, rugs, carpet, marble slabs, painting means, furniture means.
154. Use of a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143, for obtaining antibacterial, and/or antimicrobial, and/or antimycotic, and/or self-cleaning and/or anti- pollution seat means.
155. Use of a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143, for obtaining an antibacterial, and/or antimicrobial, and/or antimycotic, and/or self-cleaning and/or anti- pollution surface.
156. Use according to claim 155, wherein said surface is a wall surface.
157. Use according to claim 155, wherein said surface is a surface of an operating theatre.
158. Use according to claim 155, wherein said surface is a surface of a slaughterhouse.
159. Use according to claim 155, wherein said surface is a surface of a room of a facility chosen in a group comprising; public facilities, schools, hospitals, gymnasiums, swimming pools, public toilets, hospitals, ambulatories, refectories, canteens, restaurants, hospices .
160. Use according to claim 155, wherein said surface is a surface of a room of an industry, for example an industry chosen in a group comprising; food industry, confectionery industry, pharmaceutical industry, food packaging industry.
161. Use according to claim 155, wherein said surface is a surface of transport means.
162. Use of a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143, for reclaiming a surface.
163. Use according to claim 162, wherein said surface is chosen in a group comprising transport means surface, a wall surface for example of operating theatres, a slaughterhouses, public facilities, schools, hospitals, gymnasiums, swimming pools, public toilets, hospitals, ambulatories, refectories, canteens, restaurants, hospices, food industries, confectionery industries, pharmaceutical industries, food packaging industries.
164. Use of a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143, for obtaining footwear means .
165. Use of a cleansing product according to any one of claims 76 to 95, or according to any one of claims 106 to 143 for killing at least organisms chosen in a group comprising bacteria, fungi, sponges, viruses, mildew.
166. Use of a cleansing product according to any one of claims 76 to 95, or according to any one of claims 106 to 143, for washing skin and/or hair.
167. Use of a cleansing product according to any one of claims 76 to 95, or according to any one of claims 106 to 143, for reclaiming a surface.
168. Use according to claim 167, wherein said surface is a surface of a substrate chosen in a group comprising: tile means, panel means, furniture means, seat means, a wall surface.
169. Use according to claim 167, wherein said surface is a surface of facility chosen in a group comprising: operating theatres, slaughterhouses, public facilities, schools, hospitals, gymnasiums, swimming pools, public toilets, hospitals, ambulatories, refectories, canteens, restaurants, hospices, industries, food industries, confectionery industries, pharmaceutical industries, food packaging industries, transport means.
170. Use of a cleansing product according to any one of claims 76 to 95, or according to any one of claims 106 to 143, for killing at least a microorganism chosen in a group comprising: HSV-I (Herpes Simplex Virus-1) , Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherica CoIi, Salmonella enteridis Dl, Listeria monocytogenes, Candida albicans, Aspergillus niger, Pseudomonas, Erwinia amilovora, Xanthomonas campestris .
171. Use of a sterilising product according to any one of claims 76 to 95, or according to any one of claims 106 to 143, for sterilising surgical instruments.
172. Use of a biocide product according to any one of claims 95 to 98, or according to any one of claims 106 to 143, for treating plants, flowers, trees.
173. Use of a biocide product according to any one of claims 95 to 98, or according to any one of claims 106 to 143, for killing bacteria, fungi, mildew, sponges, viruses.
174. Use of a biocide product according to any one of claims 95 to 98, or according to any one of claims 106 to 143, organism chosen in a group comprising: Pseudomonas, Erwinia amilovora , Xanthomonas campestris .
175. Method for finishing surface means comprises at least partly coating said surface means with a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
176. Method for finishing an item comprises at least partly coating said item with a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
177. Method for making surgical instrument means comprises at least partly coating said surgical instrument means with a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
178. Method according to claim 177, wherein said partly coating comprises applying said coating product at least on active portion of said surgical instrument means intended to go in contact with a tissue of a patient.
179. Method for making prosthesis means comprises at least partly coating said prosthesis means with a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
180. Method for making filter means comprises at least partly coating said filter means with a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
181. Method according to claim 180, wherein said partly coating comprises applying said coating product at least on active surface of said filter means intended to go in contact with medium flowing through said filter means.
182. Method according to any one of claims 175 to 181, wherein said partly coating comprises spraying said coating product.
183. Method according to any one of claims 175 to 181, wherein further applying primer means before said partly coating with said coating product, it is provided for.
184. Method for preparing a topical-treatment product comprises adding a composition with the general formula AOx- (L-Me11^1.
185. Method according to claim 184, wherein said preparing comprises obtaining a topical-treatment product for treating acne diseases, and/or herpes diseases, and/or ulcers, and in particular decubitus ulcers, and/or skin irritations, and/or skin inflammations, and/or skin abrasions, and/or skin excoriations.
186. Method according to claim 184, wherein said preparing comprises obtaining a lenitive topical-treatment product .
187. Method according to claim 184, wherein said preparing comprises obtaining a cicatrizing topical-treatment product .
188. Method according to claim 184, wherein said preparing comprises obtaining a burn topical-treatment.
189. Method according to claim 184, wherein said preparing comprises obtaining a deodorizing topical-treatment product .
190. Method according to any one of claims 184 to 189, wherein said preparing comprises obtaining topical- treatment product having antiviral, and/or antibacterial, and/or antimicrobial, and/or antimycotic properties .
191. Method according to any one of claims 184 to 190, and further comprising further adding at a least quaternary ammonium salt for enhancing the properties of said topical-treatment product.
192. Method according to claim 191, wherein said further adding comprises further adding at least a chloride ammonium salt, such as benzalkonium chloride.
193. Method according to any one of claims 184 to 192, wherein said adding said composition with the general formula AOx- (L-Men+) x comprises providing Men+ selected in a group comprising Ag+ and Cu++ .
194. Method according to any one of claims 184 to 193, wherein said adding said composition with the general formula AOx- (L-Men+) x comprises further providing AOx selected in a group comprising: colloidal silica, titanium dioxide, zirconium dioxide, stannic dioxide, and zinc oxide.
195. Method according to any one of claims 184 to 193, wherein said adding said composition with the general formula AOx- (L-Men+) x comprises further providing titanium dioxide, with Titanium substantially in Anatase form as AOx.
196. Method according to any one of claims 184 to 195, wherein said adding said composition with the general formula AOx- (L-Men+) x comprises still further providing an organic and/or organometallic ligand L, preferably chosen in a group comprising: pyridine, dipyridyl, and terpyridyl, functionalized with carboxyl groups, boronic groups, or phosphonic groups; mercaptosuccinic acid, mercaptoundecanoic acid, mercaptophenol, 6- mercaptonicotinic acid, 5-carboxypentanethiol, mercaptobutyric acid, and 4-mercaptophenylboronic acid.
197. Method according to any one of claims 184 to 195, wherein said adding said composition with the general formula AOx- (L-Men+) x comprises still further providing 4-mercaptophenylboronic acid as ligand L.
198. Method according to any one of claims 184 to 197, and further comprising mixing a cationic surfactant to said composition.
199. Method according to claim 198, wherein said mixing comprises mixing a cationic surfactant chosen in a group comprising alkylammonium salts, preferably quaternary ammonium compounds, benzyl C12-C14, Ci- alkylammonium chloride, benzalkonium chloride.
200. Method according to any one of claims 184 to 199, wherein said adding comprises adding
[ (H3Tcterpy)M(CN) 3] TBA, in which H3Tcterpy is 4, 4', 4"- tricarboxy terpyridyl, TBA is tetrabutylammonium cation, M is a metal atom a which first functional group and second functional group of said ligand L are coordinated.
201. Method according to any one of claims 184 to 199, wherein said adding comprises adding [ (H3Tcterpy)M(NCS)3]TBA, in which H3Tcterpy is 4, 4', 4"- tricarboxy terpyridyl, TBA is tetrabutylammonium cation, M is a metal atom a which first functional group and second functional group of said ligand L are coordinated.
202. Method according to any one of claims 184 to 199, wherein said adding comprises adding
[M ( H3Tcterpy) (bpy) NCS ] TBA, in which H3Tcterpy i s 4, 4' , 4"-tricarboxy terpyridyl, bpy is 2, 2' -dipyridyl, TBA is tetrabutylammonium cation, M is a metal atom a which first functional group and second functional group of said ligand L are coordinated.
203. Method according to any one of claims 184 to 199, wherein said adding comprises adding M (H2dcb) 2 (NCS) 2, in which H2dcb is 2, 2 ' -dipyridyl-4, 4 ' -dicarboxylic acid, M is a metal atom a which first functional group and second functional group of said ligand L are coordinated.
204. Method according to any one of claims 184 to 203, wherein said adding comprises adding a composition having a component for killing at least a microorganism chosen in a group comprising: HSV-I (Herpes Simplex Virus-1) , Adenovirus, Poliovirus, Aviaria virus, Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherica CoIi, Salmonella enteridis Dl, Listeria monocytogenes, Candida albicans, Aspergillus niger, Pseudomonas, Erwinia amilovora, Xanthomonas campestris .
205. Method according to any one of claims 184 to 204, and further comprises further mixing additives, and/or active principle, and/or excipients suitable for obtaining a dermatological product to said composition with the general formula AOx- (L-Men+) ± .
206. Method according to any one of claims 184 to 205, and further comprises further mixing glycerin, and/or amidopropylene glycol, and/or magnesium silicate, and/or aluminum silicate and/or vaseline, and/or liquid paraffin, and/or stearyl alcohol, and/or polyethylene glycol stearate, and/or carboxypolymethylene, and/or sodium edetate to said composition with the general formula AOx-(L-Me^)1.
207. Method according to any one of claims 184 to 206, wherein said preparing comprises producing a deodorizing product.
208. Method for preparing a topical-treatment product comprises mixing together water, isopropyl palmitate, Petrolatum, Isohexadecane, Benzalkonium chloride 50%, Bees wax, PPG-15 stearylether, PEG-30 dipolyhydroxystearate, Methylparaben, Propylparaben, Citric acid, Sodium dehydroacetate, Magnesium sulphate, 2,4 Bromonitropropandiol and a composition having general AOx- (L-Men+) lr in which AOx is TiO2, Men+ is AgClO4- and L is a ligand suitable to bond both the TiO2 and AgClO4 ".
209. Method according to claim 208, wherein said preparing comprises producing an ulcer topical-treatment product.
210. Method for preparing a topical-treatment product comprises mixing together water water, PPG-15- sterarylether, Steareth-2, Cetearyl alcohol, Benzalkonium chloride, Steareth-21, Dimethicone, Methylparaben, Propylparaben, Citric acid, Sodium dehydroacetate, Butylated Hydroxyanisole (BHA) , Butylated Hydroxytoluene (BHT), 2,4 Bromonitropropandiol and a composition having general AOx-(L-Me^)1, in which AOx is TiO2, Men+ is AgClO4 " and L is a ligand suitable to bond both the TiO2 and AgClO4 ", for treating acne diseases.
211. Method according to claim 210, wherein said preparing comprises producing an acne topical-treatment product.
212. Method according to claim 211, wherein said preparing comprises producing a herpes topical-treatment product.
213. Method for preparing coating means comprises adding a coating product according to any one of claims 61 to 71, or according to any one of claims 106 to 143.
214. Method for preparing a painting product comprises adding a coating product according to any one of claims 61 to 71 or according to any one of claims 106 to 143.
215. Method according to claim 214, and further comprising further adding pigment means, and/or binder means, and/or filler means, and/or diluent means, and/or additive means
216. Method for preparing cleansing means comprises adding a cleansing product according to any one of claims 75 to 94, or according to any one of claims 106 to 143.
217. Method according to claim 216, and further comprising further adding surfactant means, and/or abrasive means, and/or pH modifying means, and/or water softener means, oxidant means, non-surfactant means, enzyme, foaming modifying means, optical brightener, and/or colour means, and/or perfume means, and/or essence means.
218. Method according to claim 216, or 217 and further comprising further adding sodium laureth sulfate, and/or glycol distearate, and/or natural oil means, and/or coconut oil, and/or inseed oil, and/or tocopherol, and/or pantothetic acid.
219. Method for preparing a sterilising product comprises adding a sterilising product according to any one of claims 76 to 94, or according to any one of claims 106 to 143.
220. Method for cleansing an item comprises bringing said item in contact with a cleansing product according to any one of claims 75 to 94, or according to any one of claims 106 to 143.
221. Method according to claim 220, wherein said bringing into contact comprises spraying said cleansing product on said item.
222. Method according to claim 220, wherein said bringing into contact comprises at least partly immersing said item into said cleansing product.
223. Method according to claim 222, wherein said at least partly immersing comprises immersing an active portion of said item into said cleansing product.
224. Method according to any one of claims 220 to 223, wherein said cleansing comprises sterilising said item.
225. Method for preparing biocide means comprises adding a biocide product according to any one of claims 95 to
98, or according to any one of claims 106 to 143.
226. Method for preparing prosthesis means comprises adding a prosthesis product according to any one of claims 99 to 101, or according to any one of claims 106 to 143.
227. Method according to claim 226, wherein said adding comprises applying said prosthesis product on surface means of said prosthesis means.
228. Method according to claim 226, or 227, wherein said adding further comprises mixing said prosthesis product to prosthesis material of said prosthesis means.
229. Method for making sanitary napkin means comprising mixing to absorbent means of said sanitary napkin means a cleansing product according to any one of claims 75 to 94, or according to any one of claims 106 to 143.
230. Method for making sanitary napkin means comprising applying on absorbent means of said sanitary napkin means a coating product according to any one of claims 61 to 71 or according to any one of claims 106 to 143.
231. Method for making sanitary napkin means comprising applying a coating product according to any one of claims 61 to 71 or according to any one of claims 106 to 143, on surface means of said sanitary napkin means intended to go in use in contact with the skin of an user of said sanitary napkin means.
232. Method according to claim 231 and further comprising mixing to absorbent means of said sanitary napkin means a cleansing product according to any one of claims 75 to 94, or according to any one of claims 106 to 143.
233. Method according to claim 231, or 232, and further comprising applying on absorbent means of said sanitary napkin means a coating product according to any one of claims 61 to 71 or according to any one of claims 106 to 143.
234. Method according to any one of claims 229 to 233, and further comprising further applying a coating product according to any one of claims 61 to 71 or according to any one of claims 106 to 143, to further surface means of said sanitary napkin means arranged opposite to surface means intended to go in use in contact with the skin of an user of said sanitary napkin means.
235. Method for sanitizing sanitary napkin means comprising applying a cleansing product according to any one of claims 75 to 94, or according to any one of claims 106 to 143 to said sanitary napkin means.
236. Method for making linen means comprises mixing to fabric means of said linen means a cleansing product according any one of claims 75 to 94, or according to any one of claims 106 to 143.
237. Method for making linen means comprising applying a coating product according to any one of claims 61 to 71 or according to any one of claims 106 to 143, to surface means of said linen means.
238. Method for sanitizing linen means comprising applying a cleansing product according to any one of claims 715 to 94, or according to any one of claims 106 to 143 to said linen means.
239. Method according to claim 233, 234, or 237, or 238, wherein said applying, and/or said further applying comprise spraying said coating product.
240. Method for making footwear means comprising applying on surface means of said footwear means a coating product according to any one of claims 61 to 71 or according to any one of claims 106 to 143.
241. Method according to claim 240, wherein said applying comprises applying said coating product on surface means of said footwear means intended to go in contact in use with a user of said footwear means.
242. Method for preparing a material comprising mixing to said material a product according to any one of claims 1 to 143.
243. Method according to claim 242, wherein said mixing comprises mixing said product to said material in a melt state.
244. Method according to claim 242, or 2437, wherein said material is chosen in a group comprising plastics, glass .
245. Method for recovering a product according to any one of claims 1 to 143 comprises contacting said product with an alcoholic solution said metal ion(s) Men+ .
246. Method according to claim 245, wherein said contacting comprises immersing said product into said solution.
247. Method according to claim 246, wherein said contacting comprises wetting said product with said solution.
PCT/EP2006/067361 2006-10-12 2006-10-12 Material, item and products comprising a composition having anti-microbial properties Ceased WO2008043396A1 (en)

Priority Applications (17)

Application Number Priority Date Filing Date Title
EP11196092.8A EP2452558B1 (en) 2006-10-12 2006-10-12 Use of a composition having anti-microbial properties
PL11196094T PL2452560T3 (en) 2006-10-12 2006-10-12 Use of a composition having anti-microbial properties
ES11196094.4T ES2487665T3 (en) 2006-10-12 2006-10-12 Use of a composition with antimicrobial properties
EP11196093.6A EP2452559B1 (en) 2006-10-12 2006-10-12 Use of a composition having anti-microbial properties
PCT/EP2006/067361 WO2008043396A1 (en) 2006-10-12 2006-10-12 Material, item and products comprising a composition having anti-microbial properties
EP06807226.3A EP2079302B1 (en) 2006-10-12 2006-10-12 Use of a composition having anti-microbial properties
EP11196094.4A EP2452560B1 (en) 2006-10-12 2006-10-12 Use of a composition having anti-microbial properties
HK10101324.3A HK1137621B (en) 2006-10-12 Material, item and products comprising a composition having anti-microbial properties
PL06807226T PL2079302T3 (en) 2006-10-12 2006-10-12 Use of a composition having anti-microbial properties
EP11196096.9A EP2452561B1 (en) 2006-10-12 2006-10-12 Use of a composition having anti-microbial properties
US12/445,307 US8389022B2 (en) 2006-10-12 2006-10-12 Material, item and products comprising a composition having anti-microbial properties
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ES06807226.3T ES2486867T3 (en) 2006-10-12 2006-10-12 Use of a composition with antimicrobial properties
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WO2014195764A1 (en) * 2013-06-06 2014-12-11 Pavia Farmaceutici S.R.L. Anionic silicon dioxide derivatives adsorbed with pharmaceutically active cations for dental use
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CN101588715B (en) 2013-07-10
EP2452561A1 (en) 2012-05-16
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ES2486867T3 (en) 2014-08-19
US20100086605A1 (en) 2010-04-08
EP2452559B1 (en) 2014-03-26
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