WO2008145175A1

WO2008145175A1 - Breathing means

Info

Publication number: WO2008145175A1
Application number: PCT/EP2007/055138
Authority: WO
Inventors: Renato Ambrogio Della Valle; Carlo Alberto Bignozzi
Original assignee: Nm Tech Nanomaterials Microdevice Technology Ltd.
Priority date: 2007-05-28
Filing date: 2007-05-28
Publication date: 2008-12-04
Also published as: EP2158006A1

Abstract

A Breathing device (10; 30; 50; 60; 80) comprises mask means (11; 31; 61; 81) suitable for being applied to a face of a user, connecting means (12, 14, 16, 17; 32, 32a, 34, 36) protruding form said mask means (11; 31; 61; 81) and arranged for keeping said mask means (11; 31; 61; 81) in contact whit said face, said mask means (11; 31; 61; 81) being provided with purifying means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51; 61, 69; 90, 91, 92) arranged for purifying a stream of air passing through said purifying means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51; 61, 69; 90, 91, 92) , and it is characterised in that said purifying means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51; 61, 69; 90, 91, 92) is provided with a nanomaterial product comprising a compound having the general formula AOx- (L-Men+)i; filtering means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51, 55; 61, 69; 90, 91, 92) for a breathing device 10; 30; 50; 60; 80) provided with purifying means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51; 61, 69; 90, 91, 92) containing a nanomaterial product comprising a compound having the general formula AOx- (L-Men+)i, in which AOx is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (O) bound 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 a parameter indicating the number of (L-Men+) groups bound to the metal oxide AOx.

Description

Breathing means

The invention relates to breathing devices, such as, for example breathing masks and breathing fabrics provided with nanomaterials and/or nanomaterial products. Moreover, the invention relates to breathing devices, such as, for example, breathing masks and breathing fabrics comprising a nanomaterial composition having antibacterial, anti-microbial, antiviral, anti-mycotic, germicide, anti- polluting and photo-remediating properties. Contagious diseases spread very fast and in a very simple manner between users of public buildings such as schools, or also buses, trains, thus giving rise to epidemic diseases. For example, influenza or other types of human respiratory infections may be transmitted between different persons in very simple manner, the virus being passed to a person through the respiratory tract, therefore by breathing and/or sneezing, and/or coughing.

Moreover, the air, particularly in urban areas, is always very polluted, and the substances present in the atmosphere are mostly very harmful to the health, and may cause many respiratory diseases such as asthma, bronchial asthma, bronchitis, or also tumours, mainly of the respiratory organs . Therefore, some persons wear breathing masks for filtering the air breathed before it arrives at the respiratory tract hoping to block any pollution of the air, and/or any microbes, and/or viruses present in the air.

Moreover, patients in hospitals may be affected by contagious disease that may be passed to the other patients, or hospital attendants, or doctors.

Moreover, for certain types of person a possible contagion could be very dangerous, for example for newborn babies, or old persons, or patients in hospitals, great care is necessary to prevent a disease passing, for example from a nurse, and/or a hospital attendant, and/or a doctor to such a person . Therefore, nurses, and/or hospital attendants, and/or doctors often wear breathing masks for filtering the air breathed in so as to try to avoid being infected by a patient having a contagious disease and/or transmitting to the patient a disease affecting them.

Known breathing devices have nevertheless many drawbacks. Known breathing devices offer only a limited barrier to a user thereof. Therefore, the protection conferred to a user by known breathing devices is very limited.

In fact, many polluting substances pass through the breathing masks together with the breathed air and reach the respiratory tract of the user. Mainly polluting substances having small molecular dimensions, which are also the most dangerous substances for the user' s health, are not blocked by known breathing devices.

Moreover, known breathing devices offer only a physical barrier to many polluting substances that is inefficacious or insufficient for blocking many polluting substances. The same applies when considering known breathing devices used in hospitals or similar facilities.

Moreover viruses, or bacteria, or other dangerous microbes have very limited dimensions and may pass through the known breathing masks together with the air breathed in and/or out, reaching the respiratory tract of the user, or respectively spreading in the external environment.

An object of the invention is to improve known breathing devices . A further object is to provide a breathing device having antibacterial, anti-microbial, antiviral, anti-mycotic, germicide, anti-polluting, photo-remediating, photocatalytic properties .

A further object is to provide a breathing device comprising a nanomaterial product and having antibacterial, anti- microbial, antiviral, anti-mycotic, germicide, anti- polluting, photo-remediating, photocatalytic properties. Another object is to provide a breathing device that is efficacious in filtering the air breathed in by a user thereof, thus preventing microbes, viruses, germs, pollen, dust, or polluting substance to reach the respiratory tract of the user.

Another object is to provide a breathing device that is efficacious in filtering the air breathed out by a user thereof, thus preventing microbes, viruses, germs, or polluting substances spreading to the external environment. A still further object is to provide a breathing fabric having antibacterial, anti-microbial, antiviral, anti- mycotic, germicide, anti-polluting, photo-remediating, photocatalytic properties. A further object is to provide a breathing fabric comprising a nanomaterial product and having antibacterial, antimicrobial, antiviral, anti-mycotic, germicide, anti- polluting, photo-remediating, photocatalytic properties. A still further object is to provide a breathing device and/or a breathing fabric, and/or filtering means for a breathing device that is safe for the health of the user, and that may contact the skin of the user without causing any damage or excoriation, or allergic reaction thereto. A still further object is to provide a breathing device and/or a breathing fabric, and/or filtering means for a breathing device provided with an antibacterial, antimicrobial, antiviral, anti-mycotic, germicide, anti- polluting, photo-remediating, photocatalytic agent that is suitable for topic use. A still further object is to provide filtering means for a breathing device having antibacterial, anti-microbial, antiviral, anti-mycotic, germicide, anti-polluting, photo- remediating, photocatalytic properties.

Another object is to provide filtering means for a breathing device having antibacterial, anti-microbial, antiviral, anti- mycotic, germicide, anti-polluting, photo-remediating, photocatalytic properties and comprising a nanomaterial product . According to a first aspect of the invention, there is provided a breathing device comprising mask means suitable for being applied to a face of a user, connecting means protruding form said mask means and arranged for keeping said mask means in contact whit said face, said mask means being provided with purifying means arranged for purifying a stream of air passing through said purifying means, characterised in that said purifying means is provided with a nanomaterial product comprising a compound having the general formula AO_x- (L-Me^)₁.

The breathing device may be chosen in a group comprising for example, face mask, artificial breathing device, gas mask, underwater mask, anaesthetic mask, protective mask, for example the masks used by workers during dangerous and probably polluting operations, such as welding, during handling dangerous and polluting or poisoning compositions, for example in laboratory, or also the masks used by doctors, or hospital attendants for protecting themselves during their work, for example during surgical operations, or many other different breathing means.

In a version, said purifying means comprises a purifying device arranged for purifying a stream of air breathed in by the user. In a further version, said purifying means further comprises a further purifying device arranged for purifying a stream of air breathed out by the user.

In another version, said purifying means comprises filtering means arranged for filtering said stream of air passing through said purifying means and breathed in by, and/or out from said user.

The filtering means may comprises tissue filtering means. The filtering means may comprises a cartridge filtering means that can be movably fixed to the breathing device and replaced when necessary. According to a second aspect of the invention, there is provided filtering means for a breathing device provided with purifying means containing a nanomaterial product comprising a compound having the general formula AO_x- (L-Meⁿ⁺) _±. The filtering means may be attached to a breathing device for filtering a stream of air passing through said breathing device breathed in by and/or out from said user, respectively before reaching the respiratory tract of the user of the breathing device, and/or before reaching the external environment . The filtering means may comprises tissue filtering means. The filtering means may comprises cartridge filtering means that can be movably fixed to the breathing device and replaced when necessary.

Owing to these aspects of the invention, it is possible to obtain a breathing device capable of remove bacteria, viruses, microbes, or other undesired and/or dangerous microorganisms, or also polluting substances, pollens, dust, from the air breathed in and/or out by a user of the breathing device. It is, therefore, possible to obtain an antibacterial, anti- microbial, antiviral, anti-mycotic, germicide, anti- polluting, photo-remediating, photocatalytic breathing device .

According to a third aspect of the invention, there is provided a breathing fabric provided with purifying means containing a nanomaterial product comprising a compound having the general formula AO_x-(L-Me¹^)₁.

According to a fourth aspect of the invention, there is provided the use of a breathing fabric provided with purifying means containing a nanomaterial product comprising a compound having the general formula AO_x-(L-Me¹^)₁ for producing a breathing device .

Owing to these aspects of invention, it is moreover possible to obtain an antibacterial, anti-microbial, antiviral, anti- mycotic, germicide, anti-polluting, photo-remediating, photocatalytic breathing fabric.

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; Meⁿ⁺ 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 (Meⁿ⁺) , and i is the number of (L-Meⁿ⁺) 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.

Owing to the features of the nanomaterial product, it is possible to homogeneously cover with the nanomaterial product a surface to which such composition is applied.

It is, therefore, possible to homogeneously cover a surface of the breathing fabric, and/or filtering means and/or of the breathing device, and in particular of the purifying means of the breathing device and/or of the filtering means. A very safe and reliable filtering means, and/or breathing device, and/or breathing fabric may thus be obtained. Moreover, the very limited particle size of the product having the general formula AO_x- (L-Meⁿ⁺) _±ι allows the product to be finely dispersed into the structure of the breathing device and/or of the filtering means, and in particular of the purifying means, therefore a breathing device and/or filtering means having homogeneous properties may be obtained. A breathing device, and/or filtering means may also be obtained in which the nanomaterial product is very homogeneously spread and, therefore, no bacteria proliferation centre can develop.

Many bacteria and/or other microorganisms are trapped by the purifying means of the breathing device, and/or filtering means, and/or on the breathing fabric, and are denaturated by the nanomaterial having general formula AO_x-(L-Me¹^)₁. Therefore, such microorganisms do not reach the user. In particular, the product having general formula AO_x- (L- Meⁿ⁺)i is capable to denature the following microorganisms: Bacteria : Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherichia coli, Salmonella enteridis Dl, Listeria monocytogenes, Neisseria Gonorrhoeae, Neisseria Meningitidis; Fungi: Candida albicans, Aspergillus niger; Viruses : Adenovirus, Poliovirus, Citomegalovirus, Enterovirus, Herpes virus, Measles virus, Orthomyxovirus, Paramyxovirus, Reovirus, Rhinovirus, Rubellavirus, Astrovirus, TSE responsible Agents, Calicivirus, Hepatitis A Virus, Hepatitis E Virus, Rotavirus, Hepatitis B Virus, Human Immunodeficiency virus (HIV), HTLV, Papovavirus, Poxvirus, Varicella Zoster Virus, Aviaria Viruses Group. Therefore, a breathing device, and/or a breathing fabric, and/or filtering means for a breathing device efficacious against at least the above mentioned microorganisms may be obtained. Similarly, many organic and inorganic polluting substances are trapped by the purifying means of the breathing device, and/or filtering means, and/or on the breathing fabric, and are decomposed, in particular such substances are oxidised, by the nanomaterial having general formula AO_x-(L-Me¹^)₁ and do not, therefore, reach the user. The organic and inorganic polluting substances are thus transformed by the oxidation reactions in compounds that are not harmful for the health of the user, for example CO2, H2O. Similar considerations apply to pollen, dust, and other substances that could be present in the air and that are noxious for humans, and that are trapped and/or transformed by the nanomaterial having general formula AO_x-(L-Me¹^)₁ and do not, therefore, reach the user.

The very limited particle size of the nanomaterial product having the general formula AO_x- (L-Meⁿ⁺) _lr allow finely disperse such product into the structure of the fabric and, therefore, a fabric having homogeneous properties can be obtained. Moreover, no bacteria and/or microorganism proliferation centre can develop into the structure of the breathing fabric. Moreover, a breathing fabric that may be widely used and that ensures excellent hygienic conditions may thus be obtained. Such a fabric may be used for many different purposes assuring excellent hygienic conditions, for example for obtaining breathing devices and/or portions thereof. Moreover, the antibacterial, antiviral, anti-mycotic, anti- polluting properties of such a breathing device, and/or filtering means, and/or breathing fabric are maintained over time. The need for subsequent treatments for reclaiming the afore mentioned properties is therefore avoided. Further, if necessary, it is possible to restore the properties of the breathing device, in case for example of depletion of the metal ion(s), for example by wetting the breathing fabric and/or the purifying means thereof, and/or filtering means, and/or the breathing device, or a part thereof, for example the purifying means of the breathing device is provided, with an alcoholic solution containing the same metal ion(s) Meⁿ⁺ present into the product having the general formula AO_x- (L-Meⁿ⁺) _± .

Furthermore, metal or metalloid oxide AO_x adhere to any different suitable substrate, and in case, by further adding a particular additive, it is possible to apply the nanomaterial product having general formula AO_x- (L-Meⁿ⁺) _± to any desired filtering means, and/or breathing device, and/or to any part thereof. It is also possible to obtain any desired fabric containing the nanomaterial product having general formula AO_x-(L-Me¹^)₁.

Furthermore, the nanomaterial product having general formula AO_x- (L-Meⁿ⁺) !, shows the anti-bacterial, anti-polluting activity in presence of light, solar or artificial, but also in absence of solar light, or of any other light source. Therefore very safe and reliable breathing device, and/or filtering means, and/or breathing fabric may be obtained that may be used in any desired condition thus maintaining the afore mentioned properties. In case, before applying such a product having general formula AO_x- (L-Meⁿ⁺) _lr a primer can be applied on a desired surface on which it is desired to apply the product, so as to enhance the adhesion of the product to the surface and to protect the surface.

Moreover, the product having general formula AO_x-(L-Me¹^)₁ can be used for obtaining suspensions either in aqueous or in other solvents, for example polar solvents.

The suspensions obtained may be applied to any desired substrate, and/or fabric, such as plastics, ceramic material, synthetic materials, natural rubber, synthetic rubber, metal, composite material, polymeric material, natural fabric, cotton, flax, synthetic fabric, engineered fabric, etc..

Further, suspensions of the product having general formula AO_x-(L-Me¹^)₁ are stable over time, and this avoids the need to mix the different components only just before applying such product, and/or a suspension thereof, on the desired substrate.

Preferably the product having the general formula AO_x- (L- Meⁿ⁺)i further comprises a quaternary ammonium salts for enhancing the antiviral, antibacterial, antimicrobial, antimycotic properties. Moreover, by suitably choosing the different elements in the product having the general formula AO_x- (L-Meⁿ⁺) _lr a product may be obtained compatible and thus mixable with any physical state, for example emulsions, gels, suspensions, foams, microbeadlets, microspheres, granules, microgranules, multiple emulsions, e.g. water-in-oil-in-water emulsions.

Moreover, the product having the general formula AO_x- (L- Meⁿ⁺)i, shows deodorizing properties, removing any smells from an air stream passing therethrough, so further improving the properties of the breathing device and/or of the breathing fabric, and/or of the filtering means according to the invention .

This further improve the quality of the air breathed in by a user wearing the breathing device according to the invention. By suitably choosing the elements in the product having general formula AO_x- (L-Meⁿ⁺) _lr it is possible to obtain products having a great cutaneous compatibility, and/or a great efficacy in deodorizing the air, and/or a great efficacy in eliminating any microbe, bacteria, virus, or other microorganisms, and/or in removing pollution.

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 AO_x- (L-Meⁿ⁺) _±;

Figure 2 is a microscope image of a product having the general structure of Figure 1. Figure 3 is a schematic view of a breathing fabric according to the invention;

Figure 4 is a frontal view of a first version of a breathing device according to the invention;

Figure 5 is a perspective view showing purifying means of the a breathing device of Figure 4;

Figure 6 is a frontal view of the purifying means in Figure

5;

Figure 7 is a frontal view of a second version of a breathing device according to the invention; Figure 8 is a lateral view of a third version of a breathing device according to the invention worn by a user;

Figure 9 is a perspective view of a fourth version of a breathing device according to the invention worn by a user;

Figure 10 is a perspective view of a cartridge filter with which the breathing device in Figure 9 is provided;

Figure 11 is an interrupted section of the cartridge filter of Figure 10;

Figure 12 is a fragmented and partially sectioned lateral view of a fifth version of a breathing device according to the invention;

Figure 13 is an enlarged sectioned view of a particular of the breathing device in Figure 12.

With reference to Figure 1 the structure of a nanomaterial product having the formula AO_x- (L-Meⁿ⁺) _x is schematically shown . 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 (Tiθ2) , zinc oxide (ZnO) , stannic oxide (Snθ2) , zirconium dioxide (Zrθ2) , and colloidal silica (Siθ2) •

In an embodiment metal oxide AO_x comprises Tiθ2, preferably with titanium prevalently in Anatase form, therefore an anti- polluting, photocatalytic composition can be obtained. The titanium dioxide has particles with an average dimension from approximately 25 nm to approximately 30 nm and a granulometric distribution that may vary in the range from approximately 5 nm to approximately 50 nm. The titanium dioxide (Tiθ2) is a semiconductor material with a crystalline structure, having a valence band separated from a conduction band by a given energy difference. Like most materials, when titanium dioxide is hit by electromagnetic radiation it absorbs energy from the radiation. When the absorbed energy is greater than, or the same as, the energy difference between the valence band and the conduction band, an electron is caused to pass from the valence band to the conduction band, generating an excess electronic charge (e^~) in the conduction band and an electron hole (h⁺) in the valence band. Solid-state titanium dioxide in crystalline form has three different allotropic forms: Anatase, Rutile, or Brookite. Anatase is the most active crystalline form from the photocatalytic point of view and has an energy difference between the valence band and the conduction band of 3.2 eV. As a result, if this material is irradiated with photons having energy greater than or the same as 3.2 eV, i.e. with an electromagnetic radiation with a wavelength the same as or less than 390 nm, an electron is caused to pass from the valence band to the conduction band. The electronic holes can oxidise most organic contaminants. Such electronic holes can, for example, react with a molecule of water (H₂O) generating a hydroxyl radical (^φ0H) that is highly reactive.

The excess electrons have very great reducing power and can react with the molecule of the oxygen to form the superoxide anion (O₂ ^") . The oxidation reaction of the water molecule is shown in the formula (i) and the reduction reaction of the oxygen is shown in the formula (ii) : TiO₂ (h⁺) + H₂O ^■* TiO₂ + 'OH + H⁺; (i)

TiO₂ (e^~) + O₂ -* TiO₂ + O₂ ^'" (ii) The hydroxyl radical (^"OH) is particularly active both for the oxidation of organic and inorganic substances, for example present in the air, mainly polluting substances, for example nitrogen oxides (NO_x) , sulphur oxides (SO_x) , or volatile organic substances, such as benzene (CeH₆) , both for deactivating microorganisms, bacteria, microbes, fungi, viruses .

In particular, the organic compounds are oxidized to carbon dioxide (CO₂) and water (H₂O) , the nitrogen compounds are oxidized to nitrate ions (Nθ3^~) , the sulphur compounds are oxidized to sulphate ions (SO₄ ^2-) .

The titanium dioxide furthermore has an anti—microbial, anti^¬ bacterial and anti-mould action that is very effective. The titanium dioxide is furthermore able to decompose under light irradiation many gases or harmful substances such as thiols or mercaptans, formaldehyde, having an unpleasant smell .

The decomposition of such gases or substances eliminates the bad smells associated therewith. Therefore, the oxidation process do not produce substances harmful for the human health.

In the molecule having general formula AO_x (L-Meⁿ⁺) _lr Meⁿ⁺ is a metal ion, preferably a metal having antibacterial, antiviral, antimycotic activity is used, for example Ag⁺, Cu⁺⁺. In the molecule having general formula AO_x (L-Meⁿ⁺) _lr L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AO_x) and the metal ion (Meⁿ⁺) , and i is the number of (L-Meⁿ⁺) 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. Preferably, the value of the parameter i, may be comprised between about 100 and 10000.

The bifunctional molecules L may be an organic molecule provided with different suitable functional groups: a first functional group binding to the AO_x oxide, and a 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, SH, 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. The bifunctional ligand L can be selected in a group comprising: nitrogen-containing heterocycles having 6 to 18 members, preferably pyridine, dipyridyl, or terpyridyl, possibly substituted with one or more substituents, selected preferably between: carboxyl (-COOH) , boronic (-B(OH)₂), phosphonic (-POaH₂) , mercaptan (-SH) , and hydroxyl (- OH) ;

Ce to Ci8 aryls, preferably selected from: phenyl, naphthyl, biphenyl, and possibly substituted with one or more substituents selected preferably between: carboxyl

(-COOH) , boronic (-B(OH)₂), phosphonic (-PO₃H₂), mercaptan (-SH) , and hydroxyl (-OH) ;

C₂ to Ci8 monocarboxylic and dicarboxylic acids, possibly substituted with one or more mercaptan groups (-SH) and/or hydroxyl groups (-OH) . 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. In a version, quaternary ammonium salts may be added to the composition having the general formula AO_x- (L-Meⁿ⁺) _x so enhancing the antiviral, antibacterial, antimicrobial, antimycotic properties of the composition. Quaternary ammonium salts, are positively charged polyatomic ions having 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 Ri-4 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-Me¹^)₁ it is possible to improve the stability of suspensions, or emulsions or solutions of the composition having the general formula AO_x- (L-Meⁿ⁺) !, and also to enhance the property thereof, increasing the antiviral, antibacterial, antimicrobial, fungicidal properties.

For example tetraalkylammonium salt, and/or alkylammonium salts, and/or benzalkonium chloride, may be added to the composition having the general formula AO_x- (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 AO_x- (L-Meⁿ⁺) _x is efficacious against several different microorganisms such as for example bacteria, fungi, sponge, mildews, and also for removing organic and inorganic polluting substances. For example efficaciousness against the Bacteria : Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherichia coli, Salmonella enteridis Dl, Listeria monocytogenes, Neisseria Gonorrhoeae, Neisseria Meningitidis; Fungi: Candida albicans, Aspergillus niger; Viruses : Adenovirus, Poliovirus, Citomegalovirus, Enterovirus, Herpes virus, Measles virus, Orthomyxovirus, Paramyxovirus, Reovirus, Rhinovirus, Rubellavirus, Astrovirus, TSE responsible Agents, Calicivirus, Hepatitis A Virus, Hepatitis E Virus, Rotavirus, Hepatitis B Virus, Human Immunodeficiency virus (HIV), HTLV, Papovavirus, Poxvirus, Varicella Zoster Virus, Aviaria Viruses Group, SARS corona virus, has been demonstrated.

As can be seen from Figure 1, several molecules of ligand L, together with several metal ions Me⁺, are bound to metal oxide AO_x and are arranged so that almost all the surface of the metal oxide AO_x 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 AO_x can be homogeneously covered by metal ion Me⁺. Furthermore, owing to the very small dimensions of the molecules contained in the nanomaterial product AO_x- (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, a fabric, a tissue, with homogeneous properties. For the same reason very homogeneous emulsions, or suspensions, or solutions in many different solvents may be obtained with the nanomaterial product AO_x- (L-Meⁿ⁺) _x. Such nanomaterial product AO_x- (L-Meⁿ⁺) _± is spread, or applied to a surface, allowing a very homogeneous coverage and/or coating of the surface to be obtained.

Moreover, nanomaterial product, and/or an emulsion, and/or a suspension, and/or a solution containing the nanomaterial product can be absorbed on a desired fabric, and/or tissue, so very homogeneously impregnating the structure of the fabric, and/or the tissue, and conferring to the fabric, and/or the tissue, antibacterial, anti-microbial, antiviral, anti-mycotic, germicide, anti-polluting, photo-remediating properties .

The fabric may be successively subjected to suitable operations for allowing any solvent and/or additive of the emulsion, and/or a suspension, and/or a solution to be evaporated.

The nanomaterial product having general formula AO_x- (L-Meⁿ⁺) _± has very reduced particle size, preferably comprised between about 200 nm and 5000 nm. Therefore very thin and homogenous films homogeneously covering a surface can be obtained.

In Figure 2 a microscope image of a particular product having the general structure of Figure 1, i.e. one of the possible molecule having formula AO_x-(L-Me¹^)₁, it is shown. In the product in Figure 2 AO_x is Tiθ2 oxide, L is an organic bifunctional ligand, and Meⁿ⁺ is Ag⁺. Such a product is named "Bactercline".

An aqueous suspension of "Bactercline", appears as a milky suspension of Titanium Dioxide crystals in water. A 50ml sample of "Bactercline" was dried under vacuum at room temperature by using a rotary pump operating at 10-3 Torr. The dried crystals were collected, deposited on microscope stubs coated with gold in an Edwards S150 Sputter Coater. Therefore the dried crystals are introduced in an analysing chamber of a microscope and analysed. A Scanning Electron Microscopy microscope of the type Cambridge Stereoscan 360, Cambridge Instrument Ltd., operating with secondary electrons at 20KV, has been used. The image obtained by the microscope has been reported in Figure 2. As can be observed in the image of Figure 2, in "Bactercline" crystal aggregates may be observed. In Figure 2 the resolution of the microscope has been indicated using the tract T corresponding to a dimension of 0.2 μm, i.e. of 200 nm.

The Figure 2 shows that the crystals of the "Bactercline" have an average dimension comprised between about 200 and 300 nm.

Therefore, the crystals of "Bactercline" have very reduced dimensions allowing a homogeneous spreading of the product n a desiderate substrate, but also at the same time, not so reduced to be considered between the harmful nanoparticles .

By suitably changing the molecule making up the product having general formula AO_x- (L-Meⁿ⁺) _x products having particle size comprised between about 150 nm and about 5000 nm, may be obtained. Therefore, very thin and homogenous films homogeneously covering a surface can be obtained.

The nanomaterial product having general formula AO_x- (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 suspensions of the nanomaterial product having general formula AO_x- (L-Meⁿ⁺) _x a metal or metalloid oxide AO_x is mixed with a Ligand L, and with a solution into which ion Meⁿ⁺ 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.

Many different commercial available forms of the based titanium dioxide products may be used for obtaining suspensions based on titanium dioxide. The afore mentioned suspensions may be transparent or opaque, or milky and would affect the colour properties of the final suspension prepared. The suspensions 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.

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 AO_x 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 AO_x and to the metal ions Meⁿ⁺, such suspensions may be used for obtaining many different products.

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 Meⁿ⁺ may be added.

In some other cases 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 Meⁿ⁺, preferably in alcoholic solution, may be added and mixed so that the absorption reactions may take place.

Cationic surfactants may also enhance the antibacterial, antimycotic, antimicrobial properties of the suspensions obtained.

The solution and/or emulsion, and/or suspension of the nanomaterial product may be added and applied to any desired substrate, in any desired material, to filtering means, fabric, tissue for obtaining breathing devices, filtering means and fabric having anti-bacterial, antimicrobial, antimycotic, self-cleaning, anti-polluting properties. The solution and/or emulsion, and/or suspension of the nanomaterial product may be added during any desired stage of a process for producing breathing devices, filtering means and fabric.

In case, the particular solvents used in the preparation of the suspension of the nanomaterial product, and or the form of the nanomaterial product may be chosen in view of a better compatibility with the substrate to which the latter has to be applied, tissues, fabric.

Example 1 Adsorption of 4-mercaptophenylboronic acid and Ag+ ions onto "TiO₂ 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 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 AO_x-(L-Me^)₁ is obtained, in which AO_x is TiO₂, L is 4- mercaptophenylboronic, and Meⁿ⁺ is Ag⁺. Similar compositions may also be obtained using methods similar to that described in which AO_x is TiO₂, Meⁿ⁺ is Ag⁺ and L is an organic bifunctional ligand, for example 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.

Such compositions are hereinafter referred to as "Bactercline" for sake of brevity. Example 2 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 "TiO₂ P25" and the consequent larger surface area of the suspended matter are responsible for the complete adsorption of the bifunctional ligand. To the transparent odourless 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 TiO₂ in a concentration of 1.5% and ethanol comprised between about 10% and 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-Me¹^)₁ is obtained, in which AO_x is TiO₂, L is 4- mercaptophenylboronic, and Meⁿ⁺ is Ag⁺, and further comprising a quaternary ammonium salt such as benzalkonium chloride. As previously stated similar suspension in which AO_x is TiO₂, and Meⁿ⁺ is Ag⁺, and L is a bifunctional ligand may also be obtained by suitably varying the molecule L of the composition having the general formula AO_x- (L-Meⁿ⁺) _x . Hereinbelow, also such suspensions 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 L ligand and of silver ions are adjusted based on the amount of titanium dioxide in the product.

For example, a product "PSO-419 D2" having a content of TiO₂ of 2% and pH ca. 2 is prepared according to the following method.

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 ⁰C 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 50%, preferably of about 25%. A transparent suspensions based on TiO₂ is therefore obtained.

The obtained product is then 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 3 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 TiC>2 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 AO_x, 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 4 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 IxIO^"4 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 TiO₂/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. Antibacterial and antiviral activity of the composition having the general formula general formula AO_x-(L-Me^)₁ has been tested, in particular with reference to products obtained according to any one of the examples 1 to 4. 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 1 and 2.

Tests have been conducted for evaluating the bactericidal, antimycotic, virucidal properties of a solution of the product containing a composition having the general formula

AO_x-(L-Me¹^)₁, in which AO_x is TiO₂, Meⁿ⁺ is Ag⁺, and L is an organic bifunctional ligand 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 1 to 4.

The bactericidal activity 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 product having the general formula AO_x- (L-Meⁿ⁺) _± 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.

Staphylococcus aureus >3.27 *10⁵ >4.02 *10⁵

Pseudomonas aeruginosa >1.23 *10⁵ >4.00 *10⁵

Escherichia coli >1.20 *10⁵ >4.00 *10⁵

Enterococcus faecalis >1.55 *10⁵ >4.19 *10⁵

Salmonella enteπdis Dl >1.21 *10⁵ >4.21 *10⁵

Listeria monocytogenes >5.56 *10⁵ >4.24 *10⁵

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. The product having the general formula AO_x-(L-Me¹^)₁ 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 the product having the general formula AO_x-(L-Me¹^)₁ 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.

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.

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.

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 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.

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.

Experiments have been conducted according to the European standard UNI EN 14476 - 2004.

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 IxIO⁶ 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.

Table 5

Moreover, experiments similar to those previously described have been also conducted, according to the European standard UNI EN 14476 - 2004, for evaluating the virucidal activity of "Bactercline" against the SARS Coronavirus, i.e. the virus that causes Severe Acute Respiratory Syndrome, Adenovirus and Poliovirus . Moreover, experiments similar to those previously described have been also conducted, according to the AFNOR NFT 72 180 - 1989 standard for evaluating the virucidal activity of "Bactercline" against the Aviaria group viruses . The experiments, the results of which have not been reported, for sake of brevity, show an extremely high virucidal activity of "Bactercline" also against SARS Coronavirus and Aviaria group viruses .

In fact the experiments show disappearance of 10⁶ of virus units after a time contact with "Bactercline" of only 15 minutes. In all cases the decimal logarithm of the virucidal activity was greater than 6, and therefore that "Bactercline" is a virucidal product.

A product having general formula AO_x- (L-Meⁿ⁺) _lr may be used for obtaining a breathing fabric provided with antibacterial, anti-microbial, antiviral, anti-mycotic, germicide, anti- polluting, photo-remediating properties.

In Figure 3 a fabric 1 according to the invention is shown. The fabric 1 is a breathing fabric, i.e. a fabric suitable for allowing gases, and/or liquid substances to pass therethrough.

The fabric 1 is provided with a plurality of layers 2 comprising a first layer 6, a second layer 4 and an intermediate layer 5 interposed between the first layer 6 and the second layer 4. The layers 4-6 of the plurality of layers 2 being bonded one to the other for forming the fabric 1, preferably by sewing or being laminated together, at bonding zones.

The different layer 4-6 of the plurality of layer 2 of the breathing fabric 1 may be different from one another or may also be made of the same material or fibres. At least one of the layers 4-6 of the plurality of layer 2 of the breathing fabric 1 comprises purifying means arranged for purifying a stream passing therethrough.

The purifying means comprises a nanomaterial product having general formula AO_x- (L-Meⁿ⁺) _± .

In a version, the at least one layer of the plurality of layer 2 of the breathing fabric 1 provided with the product having general formula AO_x- (L-Meⁿ⁺) _x is the external layer, i.e. the layer that when the fabric 1 is used for making up wearable object, such as for example a dress, or a cover dress, or a breathing mask, is intended to be positioned at the side opposite to the user.

In this way, any degradation product obtained by the degradation reactions due to the product having general formula AO_x- (L-Meⁿ⁺) _± may be easier liberated in the external environment .

In a further version, the at least one layer of the plurality of layer 2 of the breathing fabric 1 provided with the product having general formula AO_x- (L-Meⁿ⁺K is the intermediate layer 5.

In this way, any degradation process and any filtering property of the wearing object obtained with the fabric 1 may be enhanced. The product having general formula AO_x- (L-Meⁿ⁺) _lr may be for example in powder from, and/or a solution, and/or a suspension thereof.

The product having general formula AO_x- (L-Meⁿ⁺) _lr may be added to the fabric 1 at any desired preparation phase. A solution, and/or a suspension of the product having general formula AO_x- (L-Meⁿ⁺) _x may be added both by spraying it on a desired surface of the fabric, or also the fabric, and/or the cloth forming the at least one layer thereof, may be immersed in a solution, and/or a suspension of the product having general formula AO_x- (L-Meⁿ⁺) _x so as to allow the fabric to absorb and being impregnated by the nanomaterial product.

The real technique used may be chosen basing on the kind and on the features of the particular fabric to be treated. In any case, the characteristic dimension of the product having general formula AO_x- (L-Meⁿ⁺) _x allow a very homogeneous fabric according to the invention to be obtained. In a further version, a primer may be applied to the fabric 1 treated with the product having general formula AO_x- (L-Meⁿ⁺) _lr in order to enhance the adhesion of the product having general formula AO_x- (L-Meⁿ⁺) _± to the fabric, and to preserve the features of the cloth. The primer may be applied both by spraying and by immersion, and/or using any other suitable technique.

Owing to the properties of the nanomaterial product having the general formula AO_x- (L-Meⁿ⁺) _x an antibacterial, antimicrobial, antiviral, anti-mycotic, germicide, anti- polluting, photo-remediating fabric 1 may be obtained. The breathing fabric 1 may be a natural or synthetic fabric, or also a composite fabric.

The breathing fabric 1 may comprise for example, cotton, and/or hemp, and/or flax, and/or wool, and/or other natura fibers, and/or polypropylene (PP) film, PU, nylon, and/or Tetratex, and/or polytetrafluoroethylene (PTFE) , and/or Gore- Tex® produced by W. L. Gore & Associates, and/or thermoplastic polyurethane (TPU) resins such as Estane®, Permax® produced by Noveon Inc.. The breathing fabric 1 may comprise microfiber nonwoven, or a breathing microporous or monolithic film, any woven, knitted, open mesh film or nonwoven fabric, a carded web of a blend of cotton and PP staple fibre.

In a version not shown, the breathing fabric 1 may comprise a different number of layers, higher or les than three, at least one of the layers of the fabric 1 being provided with purifying means comprising a nanomaterial product having general formula AO_x-(L-Me^)₁.

The fabric may also be a one-ply fabric, the single layer thereof being provided with purifying means comprising a nanomaterial product having general formula AO_x- (L-Meⁿ⁺) _± .

The breathing fabric 1 according to the invention may be used for many different uses, for example for obtaining breathing device, or portion of the breathing device that are active in avoiding any microbe, bacteria, virus, pollen, dust, polluting substance to pass through the breathing device. The breathing fabric 1 may also be used for obtaining clothes, and/or white coats, and/or protective clothes, for example the protective clothes worn over regular clothes by workers at possibly dangerous activities, or by doctors, and/or hospital attendant during surgical operations, and/or other possibly contagious activities. With reference to Figure 4 to 6 a version of a breathing device 10 according to the invention it is shown. The breathing device 10 comprises a mask body 11 made of any desired fabric, for example a woven fabric, and wearing improving means 12 protruding form the mask body 11 and arranged for improving the wearability of the breathing device 10.

The mask body 11 may have any desired shape, and it is arranged to be positioned on the face of the user so that the air breathed in and/or out by the user passes through the mask body 11 and is filtered thereby.

The mask body 11 has a surface S so shaped has to cover a certain zone of the face of the user of the breathing device

10.

The mask body 11 is surrounded by a perimetrical zone 13 that may be in elastic material so as to improve the wearability of the breathing device 10 and the adhesion of the latter to the face of a user.

The wearing improving means 12 comprises attaching means 14 fixed to the mask body 11, preferably at the perimetrical zone 13, and arranged for attaching the breathing device 10 to a face of a user, and plurality of flaps 15 protruding from the mask body 11 and arranged to enhance the adhesion of the breathing device 10 to the face of a user. The attaching means 14 comprises a plurality of ear strings 16 protruding from the perimetrical zone 13 of mask body 11 and arranged to fix the breathing device 10 to the ears of the user. Each flap 17 of the plurality of flaps 15 is so shaped as to improve the wearability of the breathing device 10 and to avoid any gap to be formed between the breathing device 10 and the face of the user, so improving the filtering properties of the breathing device 10. Each flap 17 may be an extendable flap so further improving the wearability of the breathing device 10 and the filtering properties of the latter. The mask body 11 further comprises purifying means 18 arranged for purifying the air passing therethrough.

The purifying means 18 may be removably or fixedly attached to the mask body 11.

The purifying means 18 is so shaped as to take up a surface portion Sl of the surface S of the mask body 11, such surface portion Sl being shaped and positioned in the mask body so that any air breathed in and/or out by the user passes through the surface portion Sl.

Moreover the mask body 11 may be formed in a non breathing material, so as to further minimising the air quantity passing through the mask body 11 externally to the purifying means 18.

In this way, the purifying means 18 purifies the air breathed in by the user and/or breathed out by the user, avoiding any bacteria, virus, microbe, polluting substance, dust, pollen to reach the user of the breathing device 10.

In a version not shown, the purifying means 18 may be so shaped as to take up almost the entire surface S of the mask body 11. The purifying means 18 comprises a nanomaterial product having the general formula AO_x-(L-Me¹^)₁.

In a version, the purifying means 18 comprises a breathing fabric impregnated with a nanomaterial product having the general formula AO_x- (L-Meⁿ⁺) _± . The fabric may be a one-ply or a multi-ply fabric having at least one of the ply impregnated with the nanomaterial product having the general formula AO_x-(L-Me¹^)₁. With reference to the version in Figure 5, 6, the purifying means 18 comprises a multi-layer pad 19, that can be inserted in the structure of the mask body 11, or removably, or firmly attached thereto, for example by sewing, or welding, and that may be made of woven fabric or non-woven fabric.

The multi-layer pad 19 comprises a central layer 19a surrounded by an external layer 19b.

The pad 19 comprises a filtering device 20, for example a tissue filter, or a sponge filter, or a soft filter, that may be variously shaped and arranged for filtering the air passing therethrough.

The filtering device 20 comprises a plurality of filtering portions 21 suitably positioned in the pad 19 and so arranged as to optimize the filtering and purifying action of the purifying means 18.

In particular, the plurality of filtering portions 21 comprises a first filtering portion 22 arranged in the external layer 19b of the pad 19, preferably in correspondence of the position of the mouth of a user wearing the breathing device 10, and a second filtering portion 23 and a third filtering portion 24 both arranged in the central layer 19a of the pad 19.

The second filtering portion 23 and the third filtering portion 24 are so mutually arranged that a gap 25 is interposed therebetween, the gap being in correspondence to the position of the first filtering portion 22.

Each one of the filtering portions 22-24 of the plurality of filtering portions 21 of the filtering device 20 is impregnated with the nanomaterial product having the general formula AO_x- (L-Meⁿ⁺) _x and it is arranged to filter the air passing therethrough thus removing from the air any bacteria, microbe, virus, polluting substance, dust, pollen. When the user wears the breathing device 10, the mask body 11 is made to adhere to the user's face owing to the attaching means 14, and mostly to the plurality of flaps 17, so that the outside air can reach the respiratory tract of the user only passing through the purifying means 18. Therefore the air is absorbed, filtered, disinfected, sterilized by the purifying means 18, and many polluting substances are removed therefrom.

Similarly, the air breathed out by the user is made to pass through the purifying means 18 of the mask body 11, so being absorbed, filtered, disinfected, sterilized by the purifying means 18.

Moreover, Chitosan may be added to the nanomaterial product having the general formula AO_x- (L-Meⁿ⁺) _± of the purifying means 18, so further improving the properties of the purifying means 18.

With reference to Figure 7 a second possible version of a breathing device 30 according to the invention it is shown. The breathing device 30 comprises a mask body 31 made of any desired material, for example plastics, or metal, and/or of many different materials, and/or composite materials. The mask body is so shaped as to cover, when the breathing device 30 is worn by a user, almost completely the face of the user. The breathing device 30 further comprises wearing improving means 32 protruding form the mask body 31 and arranged for improving the wearability of the breathing device 30. The mask body 31 is so shaped to adhere to the face of the user so that almost no gap is defined between the mask body 31 and the skin of the user.

The wearing improving means 32 comprises attaching means 34 fixed to the mask body 31, preferably at suitable portions of a perimetrical zone 35 of the mask body 31, and arranged for attaching the breathing device 30 to the head of a user. The attaching means 34 comprises a plurality of adjustable straps 36 so shaped as to encircle a head of the user so as to attach thereto the breathing device 30.

The wearing improving means 32 further comprises adhering portions 33 so shaped as to almost tightly adhere to the face of the user so as to improve the adhesion of the breathing device 30 to the face of the user. The adhering portions 33 are preferably mostly arranged at a perimetrical zone 35 of the mask body 31.

The presence of the adhering portions 33 almost avoid the formation between the mask body 31 and the skin of the user of gaps that would limit the efficiency and efficacy of the breathing device 30 since unfiltered air would be introduced in or expelled from the breathing device 30 through the gaps. On the contrary, the presence of the adhering portions 33 allows avoiding the formation of gaps between the mask body 31 and the skin of the user, therefore no, or negligible quantities of unfiltered air, is introduced in and expelled from the mask body 31, as better disclosed below. The mask body 31 comprises viewing portions 37 arranged to be positioned at the eye of the user, made in transparent material so as to allow the user to see through the mask body 31.

The mask body 31 further comprises passage means 38 at which a stream of air may be introduced in or expelled from the mask body 31. The passage means 38 comprises a plurality of filtering means

39 suitably positioned on the mask body 31 to allow an optimal air circulation and arranged for purifying any stream passing therethrough so as to filter the air breathed in by the user and/or breathed out by the user. The plurality of filtering means 39 comprises a first filter

40 arranged at the nose of the user, a second filter 41 and a third filter 42 laterally arranged in relation to the nose. The first filter 40, the second filter 41, and the third filter 42 being arranged for filtering the air breathed in by the user.

The plurality of filtering means 39 further comprises an exhaust filter 43 arranged at a portion of the mask body 31 intended to be positioned at the mouth of the user for filtering the air breathed out by the user. The real position of the filters of the plurality of filters 39 may be varied at any will and chosen so as to improve the circulation of the air in the breathing device 30. Moreover, the number of filters of the plurality of filters 39 with which the mask body 31 is provided may be varied. The passage means 38 purifies the air breathed in by the user and/or breathed out by the user, removing therefrom any bacteria, virus, microbe, polluting substance, dust, pollen. Therefore almost the air introduced in and expelled from the mask body 31, passes through the passage means 38, and thus through the filtering means 39 so being purified. The filtering means 39 comprises a nanomaterial product having the general formula AO_x-(L-Me¹^)₁.

The filtering means 39 may comprise a fabric impregnated with a nanomaterial product having the general formula AO_x- (L-

Meⁿ⁺K.

The filtering means 39 may comprise cartridge filtering means better disclosed in the following with reference to Figures 10 and 11, and suitably provided with the nanomaterial product having the general formula AO_x-(L-Me¹^)₁. When the user wears the breathing device 30, the mask body 31 is made to adhere to the user's face, owing to the attaching means 34 and to the adhering portions 33, so that the outside air can reach the respiratory tract of the user only passing through the passage means 38, and therefore through filtering means 39 with which the passage means 38 is provided. Therefore, the air is absorbed, filtered, disinfected, sterilized by the filtering means 39, and polluting substances are removed therefrom.

Similarly the air breathed out by the user is made to pass through the purifying means 38 of the mask body 31, so being absorbed, filtered, disinfected, sterilized by the filtering means 39.

The breathing device 30 may be further provided accessories for improving the functionality of the breathing device and the wellness of the user, mainly if the user wears the breathing device for long period of time, for example with a microphone 44.

With reference to Figure 8 a third variant of the breathing device according to the invention it is shown. The Breathing device 50 is very similar to the breathing device in Figure 7, therefore corresponding parts have been indicated with the same reference number and will not be explained in detail. The breathing device 50 is so shaped as to adhere to the face of a user, so that almost no air, or only negligible quantities of air, can pass through possible gaps defined between the breathing device 50 and the face of the user. Therefore, almost all the air introduced in the breathing device 50, and/or discharged therefrom, flows through the passage means 38 provided with the filtering means 39. The filtering means 39 comprises a plurality of filtering portions 52 positioned at lateral zones 51 of the breathing device 50, and a filter 55 arranged at a portion of the mask body 31 intended to be positioned at the mouth of the user.

The plurality of the filtering portions 52 and the filter 55 filter the air breathed in by the user and/or breathed out by the user. The filtering portions 52 and the filter 55 purify the air breathed in by the user and/or breathed out by the user, removing therefrom any bacteria, virus, microbe, polluting substance, dust, pollen.

Each filtering portion 53 of the plurality of filtering portions 52, and/or the filter 55, comprises a nanomaterial product having the general formula AO_x-(L-Me¹^)₁.

The filtering portions 52, and/or the filter 55, may comprise a fabric impregnated with a nanomaterial product having the general formula AO_x-(L-Me¹^)₁. Each filtering portion 53, and/or the filter 55, may comprise a tissue filter absorbed with the nanomaterial product having the general formula AO_x-(L-Me¹^)₁.

Also in this case, when the user wears the breathing device 50, the outside air can reach the respiratory tract of the user only passing through the passage means 38 and therefore, only through the filtering means 39. Therefore the air is absorbed, filtered, disinfected, sterilized by the filtering means 39, and polluting substances are removed therefrom.

Similarly the air breathed out by the user is made to pass through the passage means 38 so being absorbed, filtered, disinfected, sterilized by the filtering means 39. With reference to Figure 9 a fourth variant of the breathing device according to the invention it is shown. Breathing device 60 in Figure 9 is very similar to that in Figure 4, therefore corresponding parts have been indicated with the same reference number and will not explained in detail .

The purifying means 18 of the breathing device 60 comprises cartridge purifying means 61 around which a cover 61a is wrapped.

The cartridge purifying means 61 filters and purifies any stream passing therethrough and removing therefrom many microbes, bacteria, viruses, pollen, polluting substances, dust . The cartridge purifying means 61 occupies a portion S2 of the surface S of the mask body 11, the portion S2 being so shaped and positioned to minimise the fraction of air introduced in or discharged from the breathing device 60 that is not made to pass through the breathing device 60. Preferably, the portion S2 is arranged at a portion of the breathing device 60 intended to be positioned at the mouth of the user.

Moreover, the mask body 11 may be formed in a non breathing material, so that almost no air passes therethrough, therefore, the air may pass only through the cartridge purifying means 61 of the breathing device 60.

The cartridge purifying means 61 may be fixed to the mask body 11 and removed therefrom to be substituted, for example because the cartridge purifying means 61 is damaged, or exhausted.

The cartridge purifying means 61 comprises at least a filter for filtering the air passing therethrough. The cartridge purifying means 61 comprises a the nanomaterial product having the general formula AO_x-(L-Me¹^)₁. Many different kind of cartridge purifying means 61 may be associated to the breathing device 60, for example the cartridge purifying means 61 shown in Figures 10 and 11.

In the version of Figures 10 and 11, the cartridge purifying means 61 comprises a mounting frame 62, and a purifying body 63. The mounting frame 62 has a rectangular annular shape so as to define an opening 64 into which the purifying body 63 is inserted.

The purifying body 63 is provided with connecting means 65 arranged to cooperate with further connecting means 66 with which the mounting frame 62 is provided, so as to firmly mount the purifying body 63 in the mounting frame 62. The mounting frame 62 is further provided with mounting means not shown and arranged to mount the cartridge purifying means 61 to the breathing device 60.

Gasket means may be provided between the cartridge purifying means 61 and the mounting frame 62, and/or between the mounting frame 62 and the mask body 11, so as prevent air leakage .

The gasket means allows to obtain a coupling between the cartridge purifying means 61 and the mounting frame 62, and/or between the mounting frame 62 and the mask body 11, that minimises or also eliminates gaps and/or air leakage therebetween to be formed.

The purifying body 63 is so shaped as to allow the passage of the air therethrough. The purifying body 63 comprises a rectangular portion 63a that in use is positioned to the side opposite to the user' s face, and a cylindrical portion 63b, that in use is positioned towards the user's face, the rectangular portion 63a and the cylindrical portion 63b are so mutually arranged to project to side one opposite to the other. At front plate 67 of the rectangular portion 63a, passage means 70 being defined through which air is introduced into and discharged from the purifying body 63. The purifying body 63 comprises housing means 68 into which filtering means 69 is housed.

The housing means 68, better shown in Figure 11, may extend through both the rectangular portion 63a and the cylindrical portion 63b of the purifying body 63, and may be provided with a variable number of filtering means 69, and/or a single filtering medium, or a plurality of filtering media, depending upon the design and desired end use. The filtering means 69 may be of any different desired type. Moreover, in case that a plurality of filtering means 69 is provided each filter of the plurality of filtering means 69 may be different or equal to the other.

With reference to Figure 11 an interrupted section of the purifying body 63 is shown, partially showing the housing means 68.

In the version illustrated, the filtering means 69 comprises a first filtering layer 71, a second filtering layer 72, a third filtering layer 73, and a fourth filtering layer 74. One or more layer of the filtering layer 71-74 may be impregnated with, or absorbed by a nanomaterial product having the general formula AO_x-(L-Me¹^)₁.

Moreover one or more layer of the filtering layer 71-74 may comprises a certain desired filter, for example particulate filter, desiccant filter, a activated carbon filter, a carbon monoxide catalyst filter, that is used for example if the breathing device is a smoke mask.

Contaminated air is drawn into the purifying body 63 of the cartridge purifying means 61 through the passage means 70, successively passes through the filtering means 69 at which contaminants, polluting substances, microbes, bacteria, viruses are removed.

Therefore, purified air is obtain at the output of the filtering means 69 that is then drawn into the interior of the breathing device 60 and is then introduced into the body of the user.

Similarly the air breathed out by the user if the breathing device 60 is made to flow through the cartridge purifying means 61 passing through the filtering means 69 and being purified.

In Figure 12 and 13, is partially shown a breathing device 80 that is particularly suitable to be used in artificial breathing apparatuses, and/or anaesthetic breathing apparatuses, and/or in respiratory apparatuses for pumping oxygen or air into and out of the lungs of a user. The breathing device 80 comprises an inlet tube 84 through which air pumped by a pumping apparatus, not shown, flows towards the user, as indicated by first arrow Fl, an outlet tube 85 through which air exhaled by the user is pumped out by a further pumping apparatus, not shown, and flows as indicated by second arrow F2, a mask portion 81 arranged to be positioned at the face of the user. The mask portion 81 receives the air flowing from the inlet tube 84 towards the user and the air breathed out from the user. Preferably, the mask portion 81 is so shaped as to adhere the face of the user and to cover both the nose and the mouth of the user. The mask portion 81 may comprise wearing improving means for improving the adhesion of the mask portion 81 to the face of the user.

The wearing improving means may be so shaped as to assure a good adhesion of the mask portion 81 to the face of the user. The mask portion 81 is so shaped as to define housing means 82 into which air flows, both from the lungs of the user and into the lungs of the user, the housing means 82 comprising a first housing 87 in which the inlet air flows, i.e. the air flowing to the user, and a second housing 88, arranged externally to the first housing 87in which the outlet air flows, i.e. the air flowing out from the user.

The mask portion 81 comprises first connecting means 83 for reciprocally connecting the inlet tube 84 and the first housing 87, positioned between the inlet tube 84 and the first housing 87, and second connecting means 86, positioned between the outlet tube 85 and the second housing 88, for reciprocally connecting the outlet tube 85 and the second housing 88.

The first housing 87 and the first connecting means 83 being provided internally to the second housing 88 and second connecting means 86.

In use, the air pumped towards the user flows through the inlet tube 84, the first connecting means 83, pours out into the first housing 87 flowing in the first housing 87 as indicated by the flowing arrows F4, and finally reaches the respiratory tract of the user.

Similarly, the air breathed out by the user pours out from the respiratory tract of the user, flows in the second housing 88, as indicated by the further flowing arrows F5, then flows through the second connecting means 86 into the outlet tube 85.

The breathing device 80 is provided with purifying means 90 arranged along the path of the air, so shaped as to allow the passage of the air therethrough and to purify the air passing therethrough removing therefrom any microbe, or bacteria, or virus, or dust, or any other undesired substance.

The purifying means 90 may comprise inlet filtering means 91 arranged along the path of the air pumped to the user, for example at the first connecting means 83, as shown in Figure 13, or also along the inlet tube 84, and arranged for purifying the air pumped to the user.

The purifying means 90 may further comprise outlet filtering means 92 arranged along the path of the air pumped out from the user, for example at the second connecting means 86, as shown in Figure 13, or also along the outlet tube 85, and arranged for purifying the air pumped out from the user.

The purifying means 90 comprises nanomaterial product having the general formula AO_x-(L-Me¹^)₁.

The purifying means 90 may comprise any different kind of filtering means suitable to be used in a specific case. The presence of the purifying means 90, allows the air to be purified in order to eliminate therefrom any polluting substance. Moreover providing the inlet filtering means 91 along the path of the air pumped to the user it is possible to purify the air before reaching the respiratory tract of the user, so as to remove therefrom any undesired substances. Moreover, providing the outlet filtering means 92 along the path of the air pumped out from the user, it is possible to purify the air breathed out or pumped out from the user before reaching the external environment. Therefore, any possible contagion is avoided.

Claims

1. Breathing device (10; 30; 50; 60; 80) comprising mask means (11; 31; 61; 81) suitable for being applied to a face of a user, connecting means (12, 14, 16, 17; 32, 32a, 34, 36) protruding form said mask means (11; 31; 61; 81) and arranged for keeping said mask means (11; 31; 61; 81) in contact whit said face, said mask means (11; 31; 61; 81) being provided with purifying means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51; 61, 69; 90, 91, 92) arranged for purifying a stream of air passing through said purifying means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51; 61, 69; 90, 91, 92), characterised in that said purifying means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51; 61, 69; 90, 91, 92) is provided with a nanomaterial product comprising a compound having the general formula AO_x- (L-Meⁿ⁺) _lr in which AO_x is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (O) bound to the metal (A) atom; Meⁿ⁺ is a metal ion; L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AO_x) and the metal ion (Meⁿ⁺) , and i is a parameter indicating the number of (L-Meⁿ⁺) groups bound to the metal oxide AO_x.

2. Breathing device according to claim 1, wherein said purifying means comprises an inlet purifying means (18, 19, 20; 38, 39, 40; 38, 39, 51; 61, 69; 90, 91) arranged for purifying a stream of air breathed in by the user.

3. Breathing device according to claim 1, or 2, wherein said purifying means comprises an outlet purifying means (18, 19, 20; 38, 39, 43; 38, 39, 55; 61, 69; 90, 92) arranged for purifying a stream of air breathed out by the user.

4. Breathing device according to any one of claims 1 to 3, wherein said purifying means comprises filtering means

(18, 19, 20; 38, 39, 40, 43; 38, 39, 51, 55; 61, 69; 90, 91, 92) arranged for filtering said stream of air passing through said purifying means.

5. Breathing device according to claim 4, and further comprising coupling means for coupling said filtering means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51, 55; 61, 69; 90, 91, 92) to said breathing device.

6. Breathing device according to claim 5, wherein said coupling means is so shaped as to cooperate with further coupling means of said filtering means for coupling said filtering means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51, 55; 61, 69; 90, 91, 92) to said breathing device.

7. Breathing device according to any one of claims 3 to 6, wherein said filtering means comprises a tissue filtering means (18, 19, 20; 39, 51, 52, 53) .

8. Breathing device according to any one of claims 3 to 7, wherein said filtering means comprises a cartridge filtering means (61, 63) that can be removably coupled to said breathing device.

9. Breathing device according to any one of claims 1 to 8, wherein said purifying means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51; 61, 69; 90, 91, 92) comprises fabric means impregnated with said nanomaterial product having the general formula AO_x-(L-Me¹^)₁.

10. Breathing device according to any one of claims 1 to 9, wherein said purifying means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51; 61, 69; 90, 91, 92) comprises fabric means coated with said nanomaterial product having the general formula AO_x-(L-Me¹^)₁.

11. Breathing device according to any one of claims 1 to 10, wherein said x is comprised between 1 and 2.

12. Breathing device according to any one of claims 1 to 11, wherein said AO_x is chosen between Titanium dioxide

(Tiθ2) , zinc oxide (ZnO) , stannic oxide (Snθ2) , zirconium dioxide (Zrθ2) , and colloidal silica (Siθ2) .

13. Breathing device according to any one of claims 1 to 12, wherein said AO_x comprises Titanium dioxide (Tiθ2) in Anatase form.

14. Breathing device according to any one of claims 1 to 13, wherein said AO_x comprises Titanium dioxide (Tiθ2) at approximately 80% as Anatase and at approximately 20% as Rutile.

15. Breathing device according to any one of claims 1 to 14, wherein said metal ion (Meⁿ⁺) is chosen between metals having antibacterial, and/or antiviral, and/or antimycotic activity.

16. Breathing device according to any one of claims 1 to 15, wherein said n is 1 or 2.

17. Breathing device according to any one of claims 1 to 16, wherein said metal ion (Meⁿ⁺) is chosen between silver ions Ag⁺, and/or copper ions, preferably cupric ions Cu²⁺.

18. Breathing device according to any one of claims 1 to 17, wherein said bifunctional molecule (L) is chosen between organic molecules, preferably between molecules having at least a first functional group binding to said AO_x, and a second functional group binding said Meⁿ⁺ ions.

19. Breathing device according to claim 18, wherein said first functional group may be chosen in a group comprising: carboxyl (-COOH) , carboxylate, phosphonic (- PO3H2) , phosphonate, boronic (-B(OH)₂), boronate, dipyridyl group, terpyridyl group.

20. Breathing device according to claim 19, wherein said dipyridylic or terpyridylic group is substituted by a carboxyl group, preferably in a para position with respect to the pyridine nitrogen.

21. Breathing device according to any one of claims 18 to 20, wherein said second functional may be chosen in a group comprising: Cl^", Br^", I^", S, SH, CNS^", NH₂, N, CN^", NCS^".

22. Breathing device according to any one of claims 1 to 21, wherein said bifunctional molecule (L) can be selected in a group comprising: nitrogen-containing heterocycles having 6 to 18 members, preferably pyridine, dipyridyl, or terpyridyl, possibly substituted with one or more substituents, selected preferably between: carboxyl (- COOH), boronic (-B(OH)₂), phosphonic (-PO3H2) , mercaptan (-SH) , and hydroxyl (-0H) ; Ce to Cis 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 (- OH) ; C2 to Cis 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.

23. Breathing device according to any one of claims 1 to 22, wherein said parameter i is comprised between about 100 and 10000.

24. Breathing device according to any one of claims 1 to 23, wherein said compound comprises molecule having different value of said parameter i.

25. Breathing device according to any one of claims 1 to 24, wherein said breathing device is chosen in a group comprising face mask, artificial breathing device, gas mask, underwater mask, anaesthetic mask, protective mask, protective masks used by workers during dangerous operations, welding protective masks, laboratory protective masks, protective masks for doctors, protective masks for hospital attendants, surgical protective masks.

26. Breathing device according to any one of claims 1 to 25, wherein said compound comprises at least a component having antibacterial, anti-microbial, antiviral, anti- mycotic, germicide, anti-polluting, photo-remediating, photocatalytic properties.

27. Breathing device according to any one of claims 1 to 25, wherein said nanomaterial product comprises at least a component effective in treating at least one of the following microorganisms: Bacteria: Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherichia coli, Salmonella enteridis Dl, Listeria monocytogenes, Neisseria Gonorrhoeae, Neisseria Meningitidis; Fungi: Candida albicans, Aspergillus niger; Viruses : Adenovirus, Poliovirus, Citomegalovirus, Enterovirus, Herpes virus, Measles virus, Orthomyxovirus, Paramyxovirus, Reovirus, Rhinovirus, Rubellavirus, Astrovirus, TSE responsible Agents, Calicivirus, Hepatitis A Virus, Hepatitis E Virus, Rotavirus, Hepatitis B Virus, Human Immunodeficiency virus (HIV), HTLV, Papovavirus, Poxvirus, Varicella Zoster Virus, Aviaria Viruses Group, SARS corona virus.

28. Filtering means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51, 55; 61, 69; 90, 91, 92) for a breathing device 10; 30;

50; 60; 80) is provided with purifying means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51; 61, 69; 90, 91, 92) containing a nanomaterial product comprising a compound having the general formula AO_x- (L-Meⁿ⁺K in which AO_x is a metal or metalloid oxide in which x indicates the number of the Oxygen atom(s) (O) bound to the metal (A) atom; Meⁿ⁺ is a metal ion; L is a bifunctional molecule that could bind both metal oxide or metalloid oxide (AO_x) and the metal ion (Meⁿ⁺) , and i is a parameter indicating the number of (L-Meⁿ⁺) groups bound to the metal oxide AO_x.

29. Filtering means according to claim 28, and further comprising coupling means for coupling said filtering means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51, 55; 61, 69; 90, 91, 92) to said breathing device.

30. Filtering means according to claim 28, or 29, wherein said filtering means comprises a tissue filtering means (18, 19, 20; 39, 51, 52, 53) .

31. Filtering means according to any one of claims 28 to 30, wherein said filtering means comprises a cartridge filtering means (61, 63) that can be removably coupled to said breathing device.

32. Filtering means according to any one of claims 28 to 31, wherein said purifying means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51; 61, 69; 90, 91, 92) comprises fabric means impregnated with said nanomaterial product having the general formula AO_x-(L-Me¹^)₁.

33. Filtering means according to any one of claims 28 to 32, wherein said purifying means (18, 19, 20; 38, 39, 40, 43; 38, 39, 51; 61, 69; 90, 91, 92) comprises fabric means coated with said nanomaterial product having the general formula AO_x-(L-Me¹^)₁.

34. Filtering means according to any one of claims 28 to 33, wherein said purifying means comprises an inlet purifying means (18, 19, 20; 38, 39, 40; 38, 39, 51; 61, 69; 90, 91) arranged for purifying a stream of air breathed in by the user.

35. Filtering means according to any one of claims 28 to 34, wherein said purifying means comprises an outlet purifying means (18, 19, 20; 38, 39, 43; 38, 39, 55; 61, 69; 90, 92) arranged for purifying a stream of air breathed out by the user.

36. Filtering means according to any one of claims 28 to 35, wherein said x is comprised between 1 and 2.

37. Filtering means according to any one of claims 28 to 36, wherein said AO_x is chosen between Titanium dioxide (Tiθ2) , zinc oxide (ZnO) , stannic oxide (Snθ2) , zirconium dioxide (Zrθ2) , and colloidal silica (Siθ2) •

38. Filtering means according to any one of claims 28 to 37, wherein said AO_x comprises Titanium dioxide (Tiθ2) in Anatase form.

39. Filtering means according to any one of claims 28 to 38, wherein said AO_x comprises Titanium dioxide (Tiθ2) at approximately 80% as Anatase and at approximately 20% as

Rutile.

40. Filtering means according to any one of claims 28 to 39, wherein said metal ion (Meⁿ⁺) is chosen between metals having antibacterial, and/or antiviral, and/or antimycotic activity.

41. Filtering means according to any one of claims 28 to 40, wherein said n is 1 or 2.

42. Filtering means according to any one of claims 28 to 41, wherein said metal ion (Meⁿ⁺) is chosen between silver ions Ag⁺, and/or copper ions, preferably cupric ions Cu²⁺.

43. Filtering means according to any one of claims 28 to 42, wherein said bifunctional molecule (L) is chosen between organic molecules, preferably between molecules having at least a first functional group binding to said AO_x, and a second functional group binding said Meⁿ⁺ ions.

44. Filtering means according to claim 43, wherein said first functional group may be chosen in a group comprising: carboxyl (-COOH) , carboxylate, phosphonic (- PO3H2) , phosphonate, boronic (-B(OH)₂), boronate, dipyridyl group, terpyridyl group.

45. Filtering means according to claim 44, wherein said dipyridylic or terpyridylic group is substituted by a carboxyl group, preferably in a para position with respect to the pyridine nitrogen.

46. Filtering means according to any one of claims 43 to 45, wherein said second functional may be chosen in a group comprising: Cl^", Br^", I^", S, SH, CNS^", NH₂, N, CN^", NCS^".

47. Filtering means according to any one of claims 28 to 46, wherein said bifunctional molecule (L) can be selected in a group comprising: nitrogen-containing heterocycles having 6 to 18 members, preferably pyridine, dipyridyl, or terpyridyl, possibly substituted with one or more substituents, selected preferably between: carboxyl (- COOH), boronic (-B(OH)₂), phosphonic (-PO₃H₂), mercaptan

(-SH) , and hydroxyl (-0H) ; Ce to Cis 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 (-POsH₂) , mercaptan (-SH) , and hydroxyl (- OH) ; C₂ to Cis 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.

48. Filtering means according to any one of claims 26 to 47, wherein said parameter i is comprised between about 100 and 10000.

49. Filtering means according to any one of claims 28 to 48, wherein said compound comprises molecule having different value of said parameter i.

50. Filtering means according to any one of claims 28 to 49, wherein said compound comprises at least a component having antibacterial, anti-microbial, antiviral, anti- mycotic, germicide, anti-polluting, photo-remediating, photocatalytic properties.

51. Filtering means according to any one of claims 28 to 50, wherein said nanomaterial product comprises at least a component effective in treating at least one of the following microorganisms: Bacteria : Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherichia coli, Salmonella enteridis Dl, Listeria monocytogenes, Neisseria Gonorrhoeae, Neisseria Meningitidis; Fungi: Candida albicans, Aspergillus niger; Viruses: Adenovirus, Poliovirus, Citomegalovirus, Enterovirus, Herpes virus, Measles virus, Orthomyxovirus, Paramyxovirus, Reovirus, Rhinovirus, Rubellavirus, Astrovirus, TSE responsible Agents, Calicivirus, Hepatitis A Virus, Hepatitis E Virus, Rotavirus, Hepatitis B Virus, Human Immunodeficiency virus (HIV), HTLV, Papovavirus, Poxvirus, Varicella Zoster Virus, Aviaria Viruses Group, SARS corona virus.

52. Breathing fabric provided with purifying means containing a nanomaterial product comprising a compound having the general formula AO_x-(L-Me^)₁.

53. Breathing fabric according to claim 52, wherein said product is impregnated in said breathing fabric.

54. Breathing fabric according to claim 52, or 53, wherein breathing fabric is coated with said product.

55. Breathing fabric according to any one of claims 52 to

54, wherein said x is comprised between 1 and 2.

56. Breathing fabric according to any one of claims 52 to

55, wherein said AO_x is chosen between Titanium dioxide (Tiθ2) , zinc oxide (ZnO) , stannic oxide (Snθ2) , zirconium dioxide (Zrθ2) , and colloidal silica (Siθ2) •

57. Breathing fabric according to any one of claims 52 to

56, wherein said AO_x comprises Titanium dioxide (Tiθ2) in Anatase form.

58. Breathing fabric according to any one of claims 52 to 57, wherein said AO_x comprises Titanium dioxide (Tiθ2) at approximately 80% as Anatase and at approximately 20% as Rutile.

59. Breathing fabric according to any one of claims 52 to

58, wherein said metal ion (Meⁿ⁺) is chosen between metals having antibacterial, and/or antiviral, and/or antimycotic activity.

60. Breathing fabric according to any one of claims 52 to

59, wherein said n is 1 or 2.

61. Breathing fabric according to any one of claims 52 to 60, wherein said metal ion (Meⁿ⁺) is chosen between silver ions Ag⁺, and/or copper ions, preferably cupric ions Cu²⁺.

62. Breathing fabric according to any one of claims 52 to 61, wherein said bifunctional molecule (L) is chosen between organic molecules, preferably between molecules having at least a first functional group binding to said AO_x, and a second functional group binding said Meⁿ⁺ ions .

63. Breathing fabric according to claim 62, wherein said first functional group may be chosen in a group comprising: carboxyl (-COOH) , carboxylate, phosphonic (- PO3H2) , phosphonate, boronic (-B(OH)₂), boronate, dipyridyl group, terpyridyl group.

64. Breathing fabric according to claim 63, wherein said dipyridylic or terpyridylic group is substituted by a carboxyl group, preferably in a para position with respect to the pyridine nitrogen.

65. Breathing fabric according to any one of claims 62 to 64, wherein said second functional may be chosen in a group comprising: Cl^", Br^", I^", S, SH, CNS^", NH₂, N, CN^", NCS^".

66. Breathing fabric according to any one of claims 52 to 64, wherein said bifunctional molecule (L) can be selected in a group comprising: nitrogen-containing heterocycles having 6 to 18 members, preferably pyridine, dipyridyl, or terpyridyl, possibly substituted with one or more substituents, selected preferably between: carboxyl (-COOH) , boronic (-B(OH)₂), phosphonic

(-PO₃H₂), mercaptan (-SH), and hydroxyl (-0H); C₆ to Ci₈ aryls, preferably selected from: phenyl, naphthyl, biphenyl, and possibly substituted with one or more substituents selected preferably between: carboxyl (- COOH), boronic (-B(OH)₂), phosphonic (-POsH₂), mercaptan (-SH) , and hydroxyl (-0H) ; C₂ to Cis monocarboxylic and dicarboxylic acids, possibly substituted with one or more mercaptan groups (-SH) and/or hydroxyl groups (- OH) ; 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.

67. Breathing fabric according to any one of claims 52 to

66, wherein said parameter i is comprised between about 100 and 10000.

68. Breathing fabric according to any one of claims 52 to

67, wherein said compound comprises molecule having different value of said parameter i.

69. Breathing fabric according to any one of claims 52 to

68, wherein said compound comprises at least a component having antibacterial, anti-microbial, antiviral, anti- mycotic, germicide, anti-polluting, photo-remediating, photocatalytic properties.

70. Breathing fabric according to any one of claims 52 to

69, wherein said breathing fabric is a single layer fabric .

71. Breathing fabric according to any one of claims 52 to 69, wherein said breathing fabric comprises a plurality of layers (2, 3, 4, 5) .

72. Breathing fabric according to any one of claims 52 to 71, wherein said nanomaterial product comprises at least a component effective in treating at least one of the following microorganisms: Bacteria : Legionella pneumophila, Pseudomonas aeruginosa, Staphilococcus aureus, Enterococcus faecalis, Escherichia coli, Salmonella enteridis Dl, Listeria monocytogenes, Neisseria Gonorrhoeae, Neisseria Meningitidis; Fungi: Candida albicans, Aspergillus niger; Viruses : Adenovirus, Poliovirus, Citomegalovirus, Enterovirus, Herpes virus, Measles virus, Orthomyxovirus, Paramyxovirus, Reovirus, Rhinovirus, Rubellavirus, Astrovirus, TSE responsible Agents, Calicivirus, Hepatitis A Virus, Hepatitis E Virus, Rotavirus, Hepatitis B Virus, Human Immunodeficiency virus (HIV), HTLV, Papovavirus, Poxvirus, Varicella Zoster Virus, Aviaria Viruses Group, SARS corona virus.

73. Use of a breathing fabric according to any one of claims 52 to 72 for producing a breathing device.

74. Use of a breathing fabric according to any one of claims 52 to 72 for producing a wearable object, such as for example a dress, cover dress.