Oxidizing composite material, process for preparing same, and uses thereof

Abstract

The present invention relates to an oxidizing composite material comprising a solid, inorganic and porous support, all or some of the pores of which contain cyclodextrins and / or cyclodextrin derivatives rendered oxidizing by ozone treatment. The present invention also relates to process for preparing such a material and to the uses thereof.

Description

[0001] Oxidizing composite material, its preparation process and its uses

[0002] TECHNICAL FIELD

[0003] The present invention relates to the general technical field of oxidizing materials.

[0004] More particularly, the present invention proposes an oxidizing composite material in the form of a solid composite material with (i) a porous inorganic support and (ii) cyclodextrins or cyclodextrin derivatives and, more generally, carbohydrates or carbohydrate derivatives, these cyclodextrins, these carbohydrates and their derivatives having an increased oxidizing power following their chemical modification by ozonation i.e. by treatment with ozone.

[0005] The present invention also relates to a process for preparing such an oxidizing material, as well as its uses in all applications aimed at taking advantage of its oxidizing properties.

[0006] PREVIOUS STATE OF THE ART

[0007] Oxidizing materials are used in various fields due to their ability to induce oxidation reactions. These materials offer effective and easily adaptable solutions for applications such as water disinfection, surface disinfection, textile treatment, waste treatment, plant processing, and industrial processes.

[0008] Indeed, oxidizing materials are crucial for eliminating pathogens in water. They destroy microorganisms by oxidizing their cellular components, ensuring safe and potable water. This pathogen-eliminating property can also be used for treating contaminated surfaces, both food-related and non-food-related, as well as for treating plants and animals.

[0009] Oxidizing materials can also break down complex organic contaminants into less harmful substances, which is vital for wastewater treatment and the rehabilitation of contaminated soils.

[0010] Finally, in industry, oxidizing materials are used for chemical synthesis, bleaching processes and as catalysts in various chemical reactions.

[0011] The main oxidizing materials currently used include oxygenated chlorine derivatives, permanganates, hydrogen peroxide, and ozone. Each type has its specific characteristics and is suited to particular needs. Oxygenated chlorine derivatives such as inorganic chlorites, chlorates, and perchlorates exhibit varying degrees of oxidizing power, increasing from hypochlorites to chlorates, and often have very moderate stability. For example, sodium chlorate is used as an oxidant in the mining industry during the extraction of metals such as uranium and vanadium. This compound exhibits significant environmental and oral toxicity, with the main effects being hematological and renal, justifying the discontinuation of its use as a herbicide in 2009.

[0012] Permanganates are particularly valued for their stability and therefore their long-lasting oxidizing power. Potassium permanganate, for example, is used as an oxidizing agent in a wide range of chemical reactions, both in the laboratory and in industry. It is also used in drinking water treatment and for preserving fruits and vegetables. In fact, it oxidizes ethylene to ethylene glycol, thereby halting the ripening process. However, permanganates have a lower oxidation potential than hydrogen peroxide and ozone.

[0013] Hydrogen peroxide is commonly chosen due to its ease of application and effectiveness in oxidation. However, this oxidizing compound presents storage challenges due to its inherent instability.

[0014] Ozone, while effective at destroying pathogens such as waterborne pathogens, requires specialized equipment for its production. Indeed, ozone is a gas under ambient conditions and cannot be stored due to its instability. Therefore, this molecule must be produced as needed by an ozonator, also called an "ozone generator," which produces an electrical discharge in a stream of oxygen (O2) or air, creating the ozone molecule (O3). Ozone can also be produced by other processes involving plasma or UV light, particularly at a wavelength of 185 nm. This ozone molecule has a limited lifespan, approximately twenty minutes in water under ambient conditions. It cannot be stored, for example, in a bottle, either in its pure form or as a mixture.It should be noted that the risk of explosion is high when the mixture is a blend of oxygen and ozone in which the ozone concentration exceeds 10-13 mol% and / or when this mixture is compressed to a pressure of several tens of bars. The lifespan of ozone can be extended, for example by significantly lowering the temperature (liquid nitrogen, for instance), but currently, no system exists capable of storing large quantities of ozone on a long-term basis. This storage limitation poses problems for the easy use of this gas because an on-site ozonator is required, and if one is available, the gas produced must be used immediately. Furthermore, depending on the intended applications, the need for an on-site ozonator may be considered too expensive, too cumbersome, or too technically demanding.

[0015] The very short lifespan of ozone is due to the instability of the ozone molecule: when two ozone molecules meet, they can decompose into three oxygen molecules according to the reaction 2 O3 → 3 O2. This decomposition is favored by temperature and the presence of catalytic elements such as certain solid materials, certain molecules, or certain humidity conditions. Thus, the half-life of ozone in the air is theoretically 3 days, but since this gas reacts with almost all surrounding materials, it is in practice only a few seconds. It is therefore very difficult to limit the ozone decomposition reaction, except at very low temperatures where the movement of molecules is reduced. Furthermore, pressurizing ozone increases its instability (bringing the molecules closer together) and therefore reduces its lifespan and, consequently, its oxidizing properties.

[0016] The inventors have already proposed a solution to the technical problem of ozone storage. Indeed, they have developed a process for producing an ozone storage material based on cyclodextrins and / or cyclodextrin derivatives [1] and more generally on carbohydrates and / or carbohydrate derivatives [2], such storage being possible through physical and / or chemical means. The material thus prepared is in solid form and is therefore easily handled and usable as an oxidizing agent in numerous applications.

[0017] The inventors set themselves the goal of developing an oxidizing material that is easy to prepare and use and does not have the disadvantages of currently used oxidizing materials, particularly in terms of toxicity and stability.

[0018] The inventors also set themselves the goal of proposing a material whose oxidizing power is further improved compared to that of the materials described in international application WO 2020 / 148497 Al [1] and in international application WO 2022 / 013504 Al [2],

[0019] PRESENTATION OF THE INVENTION

[0020] The present invention enables inventors to achieve the goals they have set for themselves.

[0021] Indeed, these studies have shown that it is possible to further increase the oxidizing power of the materials described in international applications WO 2020 / 148497 A1 [1] and WO 2022 / 013504 A1 [2] by combining ozonated cyclodextrins and / or cyclodextrin derivatives or carbohydrates and / or carbohydrate derivatives with a solid, inorganic, and porous support. Thus, this combination makes it possible to use, to obtain the same oxidizing power, less cyclodextrin and / or cyclodextrin derivatives or less carbohydrate and / or carbohydrate derivatives than in prior art materials, thereby reducing the cost of the oxidizing composite material according to the invention compared to that of prior art materials.

[0022] Thus, the oxidizing composite material according to the present invention has an oxidizing power at least 5 times greater or even 10 times greater than that obtained with an ozonated but unsupported cyclodextrin or cyclodextrin derivative (example 1, part lll.l below).

[0023] Furthermore, when used for antifungal applications, the oxidizing composite material according to the invention achieves complete inhibition of fungal growth, whereas inhibition is only partial when using the same quantity of cyclodextrin or cyclodextrin derivative in ozonated but unsupported form. Thus, the oxidizing composite material according to the invention allows the use of less cyclodextrin or cyclodextrin derivative to obtain the same antifungal effects as ozonated but unsupported cyclodextrin or cyclodextrin derivative (Example 1, Part III.4 below).

[0024] The oxidizing material according to the invention is in solid form and, more particularly, in the form of a porous inorganic matrix loaded with cyclodextrins and / or cyclodextrin derivatives that have undergone ozonation, or with carbohydrates and / or carbohydrate derivatives that have undergone ozonation. Such a solid material is therefore easily handled and used. Furthermore, due to its structure, it can be defined as a composite material.

[0025] Thus, the expressions "oxidizing composite material", "ozonated composite material", "oxidizing hybrid material", "ozonated hybrid material", "oxidizing inorganic / organic hybrid material" and "ozonated inorganic / organic hybrid material" are equivalent and can be used interchangeably to define the material that is the subject of the present invention.

[0026] Similarly, the expressions "composite material", "hybrid material" and "inorganic / organic hybrid material" are equivalent and can be used interchangeably to define the material used to prepare the material that is the subject of the present invention, i.e. prior to the ozonation step.

[0027] Furthermore, the oxidizing composite material according to the invention retains its oxidative properties in a durable manner since tests carried out by the inventors have shown that this material can be stored for several days at room temperature and for several months in the freezer, which corresponds to a significant improvement with regard to other oxidizing compounds such as, for example, ozone whose half-life, at room temperature, is on the order of twenty minutes in ozonated water.

[0028] The fact that the oxidizing composite material according to the invention is easily handled while guaranteeing long-term oxidizing power makes it possible to separate the place of production from the place of use, or even to consider a storage place separate from the place of production and the place of use.

[0029] All these advantages are achieved by using an oxidizing composite material, produced through a simple, easily industrialized process that does not require hazardous operating conditions and utilizes readily available and relatively inexpensive raw materials such as cyclodextrins or cyclodextrin derivatives, or carbohydrates or carbohydrate derivatives. Indeed, cyclodextrins and carbohydrates, already widely used in cosmetic and pharmaceutical formulations, are natural, non-hazardous, eco-friendly products that degrade in the environment.

[0030] Another interesting fact is that the presence of cyclodextrins or cyclodextrin derivatives or carbohydrates or carbohydrate derivatives makes it possible to obtain an oxidizing composite material which can be used as is or mixed with a solvent in which the cyclodextrins or cyclodextrin derivatives or the carbohydrates or carbohydrate derivatives dissolve and the oxidizing solution thus obtained can be used after simple sampling or after filtration or after removal of the porous inorganic support.

[0031] More particularly, the present invention relates to an oxidizing composite material, comprising a solid, inorganic, and porous support, all or part of whose pores contain cyclodextrins and / or cyclodextrin derivatives rendered oxidizing by ozone treatment. "Ozone treatment" means ozonation or contact with ozone.

[0032] The solid, inorganic, and porous support, hereinafter referred to as the solid support comprising the oxidizing composite material according to the invention, is porous. In other words, this solid support may have macropores, mesopores, and / or micropores. "Macropores" are understood to be pores or voids with an average diameter greater than 50 nm. "Mesopores" are understood to be pores or voids with an average diameter between 2 nm and 50 nm. "Micropores" are understood to be pores or voids with an average diameter less than 2 nm. Advantageously, the solid support comprising the oxidizing composite material according to the invention essentially comprises mesopores; this solid, inorganic support can therefore be defined as a mesoporous support. The porosity of the solid support comprising the oxidizing composite material according to the invention is advantageously open porosity.By "open porosity" we mean a porosity comprising pores which, on the one hand, open onto the surface of the solid support and therefore communicate with the outside of this solid support and which, on the other hand, are in communication with other pores, themselves communicating or not with the outside of this solid support.

[0033] It should be noted that the porosimetry of the solid support used in the oxidizing composite material according to the invention, namely the diameter and volume distribution of the pores, also plays a role in the maximum quantity of cyclodextrins or cyclodextrin derivatives, or carbohydrates or carbohydrate derivatives, retained in the pores. In certain embodiments, and particularly when this solid support is made of silica, the pore volume in the solid support used in the material according to the invention is greater than 0.5 mL / g 1 solid support.

[0034] Typically, the solid support included in the material according to the invention takes the form of objects with an average size between 1 µm and 1 mm, in particular between 15 µm and 800 µm, and especially between 20 µm and 600 µm. Such objects may be in the form of powders, particles, or grains. The solid support used can therefore be defined as a particulate or granular solid support.

[0035] The solid support included in the oxidizing composite material according to the invention, which may be natural or artificial, must not degrade upon contact with ozone. Thus, this solid support may, in particular, be based on:

[0036] (1) of a porous metal or metal alloy and, in particular, of bronze, stainless steel, monel, a Hastelloy-type superalloy;

[0037] (2) of a porous metal oxide and, in particular, of a transition metal oxide such as titanium oxide or zirconium oxide (or zirconia), a poor metal oxide such as aluminium oxide (or alumina), a metalloid oxide such as silicon oxide (or silica) such as diatomaceous earth or diatomite, silica glass or germanium oxide;

[0038] (3) of a porous metallic mixed oxide such as an aluminosilicate like zeolite or clinoptilolite, a phyllosilicate like vermiculite, an aluminosilicate glass, a zirconium silicate, a tin silicate or a cerium silicate;

[0039] (4) of a mixture of porous metal oxides such as a borosilicate or borosilicate glass; or

[0040] (5) of a porous ceramic such as terracotta, earthenware or stoneware. In a particular embodiment, the solid support used in the invention is made of silica (SiOz) and in particular a mesoporous silica such as commercial silicas such as, for example, a mesoporous and non-spherical silica SILIFLASH® SF300A (supplier SI LICYCLE), a mesoporous and spherical silica Siliasphere® SS300A (supplier SILICYCLE), an amorphous, precipitated and mesoporous silica Tixosil 68B® (supplier Solvay) or even diatomaceous earth (supplier NOVATERA).

[0041] In addition to the solid support, the oxidizing composite material according to the invention comprises cyclodextrins and / or cyclodextrin derivatives.

[0042] The term "cyclodextrin" refers to a cyclic oligosaccharide with the formula (CgHioOsJn) composed of n subunits of glucopyranose with the formula CgHioOs, typically linked by α-(1,4) chains, where n is an integer. The terms "cyclodextrin," "cycloamylose," "cycloglucan," "cyclomaltooside," and "Schardinger's dextrin" are equivalent and can be used interchangeably.

[0043] The cyclodextrins used in the context of the invention have an annular structure, forming a cage in the shape of a truncated cone delimiting a cavity whose size is dependent on the number n of glucopyranose subunits and which can stabilize other molecules, where n is advantageously between 6 and 35.

[0044] As particular examples of cyclodextrins usable within the framework of the present invention, we may cite cyclomaltohexaoses, cyclohexaamylose, a-cycloamylases or a-cyclodextrins (a-CD) in which n represents 6, cyclomaltoheptaoses or p-cyclodextrins (P-CD) in which n represents 7 and cyclomaltooctaoses or y-cyclodextrins (y-CD) in which n represents 8, cyclomaltononaoses in which n is equal to 9, cyclomaltoheneicosaoses in which n is equal to 21, cyclomaltodoicosaoses in which n is equal to 22 and cyclomaltohentricontaoses in which n is equal to 31.

[0045] The term "cyclodextrin derivative" refers to cyclodextrin as previously defined, chemically modified, cross-linked, immobilized, or organized into a molecular superstructure. Regardless of the specific variant, a cyclodextrin derivative used in the invention always presents a cavity capable of stabilizing other molecules.

[0046] A chemically modified cyclodextrin derivative is obtained by substituting at least one hydrogen atom and / or at least one hydroxyl radical of a cyclodextrin as previously defined with an atom or chemical group such as a halogen atom, an alkyl group, a hydroxyalkyl group, a thioalkyl group, a sulfhydryl group, an acetyl group, a silyl group, an acyl group, a sulfonyl group, an amine group, a sulfoalkyl ether group, a sulfate group, a phosphate group, a carboxyl group, a carboxylester group, a quaternary ammonium group, a glucosyl group, a maltosyl group, a chlorotriazinyl group, or a quaternary ammonium group. Depending on the chemical nature of the substituent group(s) used, the cyclodextrin derivative can be ionic or amphiphilic.

[0047] Illustrative and non-limiting examples of chemically modified cyclodextrin derivatives include randomly methylated α-CD, P-CD, or γ-CD; methyl-α-CD; methyl-α-CD; methyl-γ-CD; heptakis(2,3,6-tri-O-methyl)-P-CD; weakly methylated (2-O-methylated) α-CD, P-CD, or γ-CD at position 2; dimethylated α-CD, P-CD, or γ-CD; permethylated α-CD, P-CD, or γ-CD; perpentylated α-CD, P-CD, or γ-CD; acetylated α-CD, P-CD, or γ-CD; peracetylated α-CD, P-CD, or γ-CD; and hydroxypropylated α-CD, P-CD, or γ-CD. a hydroxyethylated a-CD, a P-CD or a y-CD; a sulfated a-CD, a P-CD or a y-CD; a phosphated a-CD, a P-CD or a y-CD; a carboxymethylated a-CD, a P-CD or a y-CD; a carboxymethyl etherized a-CD, a P-CD or a y-CD; a 3-trimethylammonium-2-hydroxypropyl-ether-a-CD; a 3-trimethylammonium-2-hydroxypropyl-ether-p-CD;3-trimethylammonium-2-hydroxypropyl-ether-γ-CD; mono-(6-mercapto-6-deoxy)-p-CD; mono-(6-amino-6-deoxy)-p-CD; heptakis(6-amino-6-deoxy)-p-CD; mono-(6-(diethylenetriamine)-6-deoxy)-p-CD; hexakis-(6-iodo-6-deoxy)-α-CD; sulfobutylether-α-CD; sulfobutylether-p-CD; sulfobutylether-γ-CD; 3-trimethylammonium-2-hydroxypropylether-α-CD; 3-trimethylammonium-2-hydroxypropylether-p-CD; 3-trimethylammonium-2-hydroxypropylether-γ-CD; glucosyl-α-CD; glucosyl-P-CD; glucosyl-γ-CD; maltosyl-a-CD; maltosyl-P-CD; maltosyl-y-CD; chlorotriazinyl-a-CD; chlorotriazinyl-p-CD; and chlorotriazinyl-y-CD.;

[0048] A crosslinked cyclodextrin derivative is typically obtained by forming bonds between cyclodextrins or chemically modified cyclodextrins as previously defined, using a crosslinking agent such as epichlorohydrin, 1,4-butanedioldiglycidyl ether, 1,2-epoxypropane, 1,3-diglycidylglycerol, 1,4-phenyldiisocyanate, 2,4-toluene diisocyanate, glutaraldehyde, or citric acid. A crosslinked cyclodextrin derivative can be in the form of a soluble or insoluble polymer, such as crosslinked gels or hydrogels. Thus, cyclodextrin polymers are examples of crosslinked cyclodextrin derivatives. This type of derivative can be prepared in two steps with, firstly, crosslinking of the CD molecules by epichlorohydrin in the presence of another cationic crosslinking agent and then carboxymethylation of the crosslinked particles on the surface.As a particular example, one can cite an amphoteric gel of cyclodextrins crosslinked by epichlorohydrin in the presence of 3-chloride-2-hydroxypropyl trimnethylammonium, and carboxymethylated.

[0049] An immobilized cyclodextrin derivative corresponds to cyclodextrins or chemically modified cyclodextrins as previously defined, grafted onto polymers such as polyalkylamines, polyethylene imines, polyallylamines or polyacrylates; onto membranes such as supported liquid membranes or dense membranes; onto textiles; onto inorganic beads such as silica or activated carbon beads; or onto organic resins.

[0050] Illustrative and non-limiting examples of immobilized cyclodextrin-type derivatives include poly(vinyl acetate)-p-CD membranes crosslinked with di-epoxide, polysiloxane-p-CD mixed membranes on ceramic membrane, poly(vinyl acetate)-a-CD membranes crosslinked with hexamethylene diisocyanate, P-CDs fixed on polyacrilonitrile or polyester fibers, CDs grafted onto chitosan, monochlorotriazinyl-P-CDs fixed on cotton, cotton / polyurethane or cotton / polyamide fibers and wool, cellulose or poly(ethylene terephthalate) fibers treated with the p-CD / 1,2,3,4-butanetetracarboxylic acid system.

[0051] Examples of cyclodextrin-type derivatives organized in molecular superstructure include polyrotaxanes and polypseudorotaxanes consisting of a poly(ethylene glycol) chain forming the stator complexed with several cyclodextrins forming the mobile part or rotor and the molecular tubes.

[0052] In the oxidizing composite material according to the invention, (i) a set of identical or different cyclodextrins, (ii) a set of identical or different cyclodextrin derivatives, or (iii) a set of identical or different cyclodextrins and identical or different cyclodextrin derivatives can be implemented.

[0053] Advantageously, the cyclodextrins and / or cyclodextrin derivatives used in the present invention are chosen from the group consisting of α-CDs, P-CDs, γ-CDs, hydroxypropyl α-CDs, hydroxypropyl P-CDs, hydroxypropyl γ-CDs, dimethyl α-CDs, dimethyl P-CDs, dimethyl γ-CDs; sulfobutyl ether-α-CDs, sulfobutyl ether-γ-CDs, sulfobutyl ether-γ-CDs, sulfated α-CDs, sulfated P-CDs, sulfated γ-CDs, phosphated α-CDs, phosphated P-CDs, phosphated γ-CDs; carboxymethylated a-CDs, carboxymethylated P-CDs, carboxymethylated y-CDs, carboxymethyl etherized a-CDs, carboxymethyl etherized P-CDs, carboxymethyl etherized y-CDs, 3-trimethylammonium-2-hydroxypropyl ether-a-CD; 3-trimethylammonium-2-hydroxypropyl ether-CD; 3-trimethylammonium-2-hydroxypropyl ether-y-CD; and mixtures thereof.

[0054] In the oxidizing composite material according to the invention, cyclodextrins and / or cyclodextrin derivatives are located in all or part of the pores of the solid support of this material. Advantageously, the surface of this solid support is free of cyclodextrins and / or cyclodextrin derivatives. In other words, the mass percentage of cyclodextrins and / or cyclodextrin derivatives present at the surface of the solid support is less than 10%, in particular less than 5%, and especially less than 1%, relative to the total mass of cyclodextrins and / or cyclodextrin derivatives contained in the oxidizing composite material according to the invention.

[0055] In the oxidizing composite material according to the invention, cyclodextrins and / or cyclodextrin derivatives are in solid form and in particular in crystalline, pseudocrystalline or amorphous form.

[0056] In the oxidizing composite material according to the invention, the cyclodextrins and / or cyclodextrin derivatives are rendered oxidizing following ozone treatment. By "rendered oxidizing following ozone treatment," it is meant that the cyclodextrins and / or cyclodextrin derivatives present in pores of the solid support have reacted chemically with ozone and have been chemically modified by the grafting of oxidizing functions following ozone treatment, i.e., ozonation. These can be referred to as ozonated cyclodextrins and / or cyclodextrin derivatives.

[0057] In other words, the oxidizing composite material according to the invention comprises a solid, inorganic, porous support, all or part of whose pores contain cyclodextrins and / or cyclodextrin derivatives chemically modified by grafting or introduction of at least one oxidizing function following ozonation.

[0058] For the purposes of this invention, "oxidizing functions" are defined as groups comprising at least two adjacent oxygen atoms bonded together (-OO-). These oxidizing functions can be grafted onto or introduced into the structure of cyclodextrins or cyclodextrin derivatives. In the present invention, the oxidizing functions are specifically selected from the group consisting of a percarbonic group (-C(=O)-O-OH), a hydroperoxide group (RO-OH), an organic peroxide group (R'-OOR), a trioxide group (ROO-OH), a molozonide group, an ozonide group, and a diperoxide group. In the semi-developed formulas described above, R and R' are organic groups belonging to the structure of the chemically modified cyclodextrin or cyclodextrin derivative.

[0059] Typically, cyclodextrins and cyclodextrin derivatives exhibit, following ozonation, one or more oxygenated functional groups comprising at least one oxygen atom, and in particular one or more oxidizing functional groups, identical or different, grafted onto the backbone of the cyclodextrins and cyclodextrin derivatives or introduced into the backbone structure of the cyclodextrins and cyclodextrin derivatives. It is evident that, for cyclodextrin derivatives, which are chemically modified cyclodextrins, ozone treatment increases the number of oxygenated functional groups, and especially oxidizing functional groups, present on the backbone of the cyclodextrin derivatives.

[0060] Following the ozonation of cyclodextrins and cyclodextrin derivatives, free molecules can be created. These are typically found adsorbed onto the porous inorganic support, stabilized within its pores, or stabilized within the cavities of the cyclodextrins and / or cyclodextrin derivatives. Some of these free molecules can be oxidizing agents, such as hydrogen peroxide, peracetic acid, performic acid, and trioxidane. Furthermore, following the ozonation of cyclodextrins and cyclodextrin derivatives, some of the bonds in their backbones can be modified and / or broken.

[0061] As previously mentioned, the oxidizing composite material according to the invention may comprise not cyclodextrins and / or cyclodextrin derivatives but, more generally, carbohydrates and / or carbohydrate derivatives.

[0062] The term "carbohydrate" refers to an organic compound with at least three carbon atoms comprising a carbonyl group (aldehyde or ketone) or equivalent group and at least two hydroxyl groups (-OH). An "equivalent group to a carbonyl group" refers to an acetal or hemiacetal group.

[0063] Among the carbohydrates that can be used in the context of the present invention, we can mention the oses also known as "simple carbohydrates" or "monosaccharides" and the osides also known as "complex carbohydrates" corresponding to polymers of oses linked by alpha or beta glycosidic bonds and among which we find oligosaccharides and polysaccharides.

[0064] By "carbohydrate derivative" we mean a monosaccharide derivative, an oligosaccharide derivative or a polysaccharide derivative.

[0065] By “monosaccharide”, we mean a sugar comprising 3 to 9 carbon atoms, this sugar being able to be of L or D configuration.In particular, the monosaccharides usable within the framework of the present invention are notably 3-carbon sugars (or trioses) such as glyceraldehyde and dihydroxyacetone; 4-carbon sugars (or tetroses) such as erythrose, threose and erythrulose; 5-carbon sugars (or (deoxy)pentoses) such as deoxyribose, ribose, arabinose, xylose, lyxose, ribulose and xylulose; 6-carbon sugars (or (deoxy)hexoses) such as ai lose, altrose, galactose, glucose, dextrose, gulose, idose, mannose, talose, fructose, psicose, sorbose, tagatose, fucose and rhamnose; 7-carbon sugars (or heptoses) such as sedoheptulose and mannoheptulose; 8-carbon sugars (or octoses) such as heptahydroxyoctanal and 9-carbon sugars (or nonoses) such as neuraminic acid or sialic acid.More particularly, the monosaccharides usable within the framework of the present invention are chosen from the group consisting of deoxyribose, ribose, arabinose, xylose, ribulose, galactose, glucose, dextrose, mannose, fructose, fucose and rhamnose.

[0066] By "monosaccharide derivative" or "ose derivative" is meant a ose as previously defined in which at least one hydrogen atom and / or at least one hydroxyl radical and / or the carbonyl function of a ose as previously defined is substituted by an atom or chemical group such as a halogen atom, an alkyl group, a hydroxyalkyl group, a thioalkyl group, a sulfhydryl group, an acetyl group, a silyl group, an acyl group, a sulfonyl group, an amine group, a sulfoalkyl ether group, a sulfate group, a phosphate group, a carboxyl group, a carboxylester group, a quaternary ammonium group, a glucosyl group, a maltosyl group, a chlorotriazinyl group or a quaternary ammonium group.As particular examples of monosaccharide derivatives that can be used in the context of the present invention, the following may be cited: gluconic acid, glucuronic acid, mannuronic acid, guluronic acid, galacturonic acid, iduronic acid, ascorbic acid (or oxo-3-gulofuranolactone), glucosamine, N-acetylglucosamine, N-acetylmannuronic acid, sucralose, erythritol, xylitol, arabitol (or lyxitol), ribitol (or adonitol), sorbitol (or gulitol), dulcitol (or galactitol), mannitol and volemitol.

[0067] The term "oligosaccharide" refers to a polymer of monosaccharides and / or monosaccharide derivatives, identical or different, each comprising 3 to 9 carbon atoms, and in particular 5 to 9 carbon atoms, in which the number of monosaccharides is determined and greater than or equal to two. Examples of oligosaccharides usable within the scope of the present invention include disaccharides (or diholosides), trisaccharides (or triholosides), tetrasaccharides (or tetraholosides), and oligosaccharides with 5 or more monosaccharides.

[0068] The term "disaccharide" refers to a compound formed by two identical or different monosaccharides, two identical or different monosaccharide derivatives, or one monosaccharide and one monosaccharide derivative, each comprising from 3 to 9 carbon atoms, and in particular from 5 to 9 carbon atoms. Among the disaccharides usable within the scope of the present invention are reducing disaccharides such as lactose, maltose, cellobiose, and isomaltose, and non-reducing disaccharides such as sucrose and trehalose. More specifically, the disaccharides usable within the scope of the present invention are selected from among the reducing disaccharides, and in particular from the group consisting of lactose, maltose, cellobiose, and isomaltose.

[0069] The term "trisaccharide" refers to a compound formed by three identical or different monosaccharides, three identical or different monosaccharide derivatives, two identical or different monosaccharides and one monosaccharide derivative, or one monosaccharide and two identical or different monosaccharide derivatives, each comprising from 3 to 9 carbon atoms, and in particular from 5 to 9 carbon atoms. Examples of trisaccharides usable within the scope of the present invention include acarbose, erlose (or glucosylsucrose), fucosyllactose, lactosucrose, isokestose, isomaltoristotriose, inulotriose, p-glucotriose, kestose, maltotriose, nigerotriose, panose, raffinose, rhamninose, theanderose, melezitose, and gentianose.

[0070] The term "tetrasaccharide" means a compound formed from four monosaccharides, identical or different; four monosaccharide derivatives, identical or different; one monosaccharide and three monosaccharide derivatives, identical or different; two monosaccharides, identical or different; and two monosaccharide derivatives, identical or different; or three monosaccharides, identical or different, and one monosaccharide derivative, each comprising from 3 to 9 carbon atoms, and in particular from 5 to 9 carbon atoms. Examples of tetrasaccharides usable within the scope of the present invention include lychnose (or 1-α-galactosylraffinose), maltotetraose, nigerotetraose, nystose, sesamose, and stachyose.

[0071] An oligosaccharide of 5 or more monosaccharides is defined as a polymer of monosaccharides and / or monosaccharide derivatives, identical or different, each comprising from 3 to 9 carbon atoms, and in particular from 5 to 9 carbon atoms, in which the total number of monosaccharides and monosaccharide derivatives is determined to be greater than or equal to five. Such an oligosaccharide may be linear, branched, or cyclic. A particular example of an oligosaccharide of 5 or more monosaccharides is cyclodextrin as previously defined.

[0072] The carbohydrates used in the context of the present invention may also be polysaccharides. By "polysaccharide" is meant a polymer of monosaccharides, identical or different, and / or derivatives of monosaccharides, identical or different, each comprising from 3 to 9 carbon atoms and in particular from 5 to 9 carbon atoms in which the number of monosaccharides and / or derivatives of monosaccharides is indeterminate and typically greater than 10 and in particular greater than 20.

[0073] Among the polysaccharides usable within the framework of the present invention, a distinction is made between polysaccharides consisting of the same sugar or the same sugar derivative, i.e. polymers of identical sugars or derivatives of identical sugars, also designated under the names "homopolysaccharides" or "homoglycans", and polysaccharides formed of sugars and sugar derivatives, of different sugars and / or different sugar derivatives, i.e. polymers of sugars and sugar derivatives, of different sugars and / or different sugar derivatives, also designated under the names "heteropolysaccharides" or "heteroglycans".

[0074] Among the homopolysaccharides that can be used in the context of the present invention, fructans; glucans (or dextran); galactans such as agar-agar and carrageenans; xylans; mannans; amyloses; amylopectins; celluloses; chitins; starches and glycogens may be mentioned.

[0075] Among the heteropolysaccharides that can be used in the context of the present invention, we can mention hemicelluloses, acacia gum, guar gum, alginates, xanthan gums, chitosans, hyaluronic acids and xyloglucans.

[0076] Furthermore, depending on the architecture of their chain, polysaccharides can be (i) linear such as, for example, celluloses or amyloses; (ii) branched such as, for example, amylopectins, dextran or hemicelluloses or (iii) mixed such as starches and glycogens.

[0077] By "oligosaccharide or polysaccharide derivative" is meant an oligosaccharide or polysaccharide as previously defined in which at least one hydrogen atom and / or at least one hydroxyl radical and / or at least one carbonyl function is substituted by an atom or chemical group such as a halogen atom, an alkyl group, a hydroxyalkyl group, a thioalkyl group, a sulfhydryl group, an acetyl group, a silyl group, an acyl group, a sulfonyl group, an amine group, a sulfoalkyl ether group, a sulfate group, a phosphate group, a carboxyl group, a carboxylester group, a quaternary ammonium group, a glucosyl group, a maltosyl group, a chlorotriazinyl group or a quaternary ammonium group.As particular examples of oligosaccharide or polysaccharide derivatives usable within the framework of the present invention, we may mention maltitol, isomaltitol, lactitol as well as oligosaccharides and polysaccharides as previously defined, substituted by at least one hydroxyalkyl group and in particular by at least one hydroxypropyl group.

[0078] As more specific examples of oligosaccharide or polysaccharide derivatives usable within the framework of the present invention, the following may be mentioned: hydroxypropylcelluloses; hydroxypropylmethylcelluloses; hydroxypropylfructans; hydroxypropylglucans (or hydroxypropyldextrans); hydroxypropylgalactans such as agar-agar substituted with at least one hydroxypropyl group and carrageenans substituted with at least one hydroxypropyl group; hydroxypropylxylans; hydroxypropylmannans; hydroxypropylamyloses; hydroxypropylamylopectins; hydroxypropylchitins; hydroxypropyl starches; hydroxypropylglycogens; hydroxypropylhemicelluloses; acacia substituted with at least one hydroxypropyl group; guar gum substituted with at least one hydroxypropyl group; hydroxypropylalginates; hydroxypropylxanthanes; hydroxypropylchitosans;hyaluronic acids substituted with at least one hydroxypropyl group and hydroxypropylxyloglucans.;

[0079] In a particular embodiment, the carbohydrates and / or carbohydrate derivatives used in the context of the present invention are oligosaccharides, oligosaccharide derivatives, polysaccharides and / or polysaccharide derivatives.

[0080] Advantageously, when the oligosaccharide derivative is a cellulose derivative, the latter is a cellulose in which at least one hydrogen atom and / or at least one hydroxyl radical and / or at least one carbonyl function is substituted by an atom or chemical group such as a halogen atom, an alkyl group, a hydroxyalkyl group, a thioalkyl group, a sulfhydryl group, an acetyl group, a silyl group, an acyl group, a sulfonyl group, an amine group, a sulfoalkyl ether group, a sulfate group, a phosphate group, a carboxyl group, a quaternary ammonium group, a glucosyl group, a maltosyl group, a chlorotriazinyl group, or a quaternary ammonium group.

[0081] In particular, the carbohydrates and / or carbohydrate derivatives used in the present invention are different from cellulose esters.

[0082] The process according to the present invention involves implementing (i) a set of identical or different carbohydrates belonging to the same family or different families selected from monosaccharides, oligosaccharides, and polysaccharides as previously defined, (ii) a set of identical or different carbohydrate derivatives belonging to the same family or different families selected from monosaccharide derivatives, oligosaccharide derivatives, and polysaccharide derivatives as previously defined, or (iii) a set of identical or different carbohydrates belonging to the same family or different families selected from monosaccharides, oligosaccharides, and polysaccharides as previously defined and a set of identical or different carbohydrate derivatives belonging to the same family or different families selected from monosaccharide derivatives.oligosaccharide derivatives and polysaccharide derivatives as previously defined. Furthermore, in variants (i) to (iii) above, the carbohydrates and / or carbohydrate derivatives used may be used in mixtures with cyclodextrins and / or cyclodextrin derivatives as previously defined.

[0083] Everything previously described for cyclodextrins and cyclodextrin derivatives in the oxidizing composite material according to the invention applies mutatis mutandis to carbohydrates and carbohydrate derivatives. The same applies to the following regarding the process for preparing the solid oxidizing material according to the invention and its various uses.

[0084] The present invention also relates to a method for preparing such an oxidizing composite material comprising a) impregnating a solid, inorganic, porous support as previously defined with a solution comprising cyclodextrins and / or cyclodextrin derivatives; b) drying the impregnated solid inorganic support obtained in step a) thereby obtaining a composite material consisting of a solid inorganic support in which all or part of the pores contain cyclodextrins and / or cyclodextrin derivatives; and then c) contacting the composite material obtained in step b) with a gas comprising ozone thereby obtaining an oxidizing composite material.

[0085] Step a) involves using a solution comprising cyclodextrins and / or cyclodextrin derivatives. This solution therefore includes a solvent in which the cyclodextrins and / or cyclodextrin derivatives are soluble and stable. Typically, the solvent for the solution used in step a) is chosen from the group consisting of water, alcohols such as ethanol, methanol, isopropanol, and benzyl alcohol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and mixtures thereof. Advantageously, the solvent for the solution used in step a) is water. A person skilled in the art will be able to determine, without inventive effort, the quantity of cyclodextrins and / or cyclodextrin derivatives to be used in the solution used in step a) of the process according to the invention, particularly based on their solubility in the solvent of that solution.

[0086] Any impregnation technique known to a person skilled in the art can be used in step a) of the process according to the invention. This technique is in particular chosen from the group consisting of (i) the pore volume impregnation (PVI) technique in which an exact quantity of the impregnation solution is used to fill the pore volume of the support, (ii) the wet impregnation (Wl) technique in which an excessive quantity of the solution is used, and (iii) the dry impregnation (DI) technique, also called nascent wet impregnation (IWI) when the impregnated particles retain their dry character on a macroscopic scale.

[0087] Advantageously, the impregnation technique used in step a) of the process according to the invention is the pore volume impregnation (PVI) technique, and in particular a pore volume impregnation technique employing a volume of solution comprising cyclodextrins and / or cyclodextrin derivatives that is less than the pore volume of the solid, inorganic, and porous support used in this step. Specifically, the volume of solution comprising cyclodextrins and / or cyclodextrin derivatives corresponds to less than 95%, and advantageously to approximately 85% (i.e., 85% ± 5%), of the pore volume of the solid, inorganic, and porous support used. From a qualitative standpoint, this technique clearly offers several advantages over the W1 method. The main advantages are the absence of impregnation solution loss, the absence of an additional filtration step, and the dry appearance of the impregnated solid support, which is very easy to handle.

[0088] Step a) of the process according to the invention may include at least one manual or mechanical stirring and / or at least one sonication. It is the assembly consisting of the solution comprising cyclodextrins and / or cyclodextrin derivatives and the solid support that is manually stirred and / or subjected to sonication. Such a protocol promotes and facilitates the introduction and diffusion of the solution comprising cyclodextrins and / or cyclodextrin derivatives into the pores of the solid support. Advantageously, step a) of the process according to the invention may include at least one sequence of manual stirring followed by sonication and, in particular, two sequences of manual stirring followed by sonication. During this sequence or these sequences, the duration of sonication is between 5 and 30 minutes, and in particular on the order of 10 minutes (i.e., 10 minutes ± 3 minutes) or on the order of 15 minutes (i.e., 15 minutes ± 3 minutes).Furthermore, the process according to the invention may include a preliminary step to step a) of bringing the solid support into contact with the solution comprising cyclodextrins and / or cyclodextrin derivatives, intended to remove all or part of the water molecules on the surface of the porous inorganic solid support and / or contained within the pores of this solid support. By way of example, such a treatment may be a heat treatment or a vacuum extraction. As a specific example of a heat treatment usable during this preliminary step, one may cite a heat treatment at a temperature of approximately 110°C (i.e., 110°C ± 10°C) for a duration of approximately 24 h (i.e., 24 h ± 3 h).

[0089] Any drying technique known to those skilled in the art and enabling the removal of the solvent from the solution comprising cyclodextrins and / or cyclodextrin derivatives and obtaining, in all or part of the pores of the solid support, cyclodextrins and / or cyclodextrin derivatives in solid form is usable during step b) of the process according to the invention.

[0090] In a first embodiment, step b) consists of drying the solid support impregnated with the solution containing cyclodextrins and / or cyclodextrin derivatives in an oven. Those skilled in the art will be able to determine, without inventive effort, the temperature to be used during this step and, based on this temperature, the duration of this drying step. Typically, this oven drying step, and in particular this air drying step, is carried out, especially when the solvent is water, at a constant temperature between 40°C and 120°C and, in particular, between 50°C and 110°C, for a duration of between 18 h and 100 h and, in particular, between 24 h and 96 h.

[0091] In a second advantageous embodiment, step b) consists of freeze-drying the solid support impregnated with the solution containing cyclodextrins and / or cyclodextrin derivatives. The principle is the desiccation of the product via a sublimation process: the solvent is extracted from the wet product (solid support impregnated with the solution containing cyclodextrins and / or cyclodextrin derivatives), initially frozen, by directly converting this frozen solvent from a solid to a gaseous state. This is achieved by placing the sample under vacuum and then slowly increasing the temperature. The advantage is working at a sufficiently low pressure to successfully sublimate the solvent while maintaining low temperatures. As a result, the products undergo virtually no alteration during freeze-drying.

[0092] Typically, during this freeze-drying process, the solid support impregnated with the solution comprising cyclodextrins and / or cyclodextrin derivatives, and in particular with an aqueous solution comprising cyclodextrins and / or cyclodextrin derivatives, is frozen at a temperature of around -25°C (i.e. -25°C ± 5°C) for a period of between 6 h and 18 h, and in particular around 12 h (i.e. 12 h ± 3 h). The freeze-drying of this frozen product is carried out at a temperature between -100°C and -120°C and in particular around -110°C (i.e. -110°C ± 5°C), under a pressure between 0.01 mbar and 1 mbar and in particular around 0.1 mbar (i.e. 0.1 mbar ± 0.05 mbar) and for a duration between 18 h and 30 h and in particular around 22± 2 h).

[0093] Advantageously, the ozone-containing gas used in step c) of the process according to the invention is a gaseous mixture comprising ozone and at least one other gas such as oxygen, carbon dioxide, nitrogen, or a mixture thereof. When the gaseous mixture comprises ozone and oxygen, this mixture is produced from an ozone generator or ozonator, typically supplied with ambient air, dry air, humid air, compressed air, or pure oxygen. The ozone concentration in the gaseous mixture exiting the ozone generator can be constant or variable during step c). Typically, it is between 2 g / Nm³ 3 and 180 g / Nm 3 , particularly between 3 g / Nm 3 and 150 g / Nm 3 and, in particular, between 30 g / Nm 3 and 120 g / Nm 3. Ozone production in such an ozone generator or ozonator may involve an electrical discharge, a plasma or UV light, particularly at a wavelength of 185 nm.

[0094] In the process according to the invention, the contact between the composite material, i.e., the inorganic solid support loaded with cyclodextrins and / or cyclodextrin derivatives and dried in step b), and the ozone-containing gas is carried out at a temperature that may be constant or variable during step c). Typically, this temperature is between 0°C and 80°C, in particular between 5°C and 70°C, especially between 10°C and 60°C, more particularly between 15°C and 55°C, and even more particularly between 15°C and 40°C. Thus, this contact can be carried out at ambient temperature. "Ambient temperature" means any temperature between 18°C ​​and 28°C.

[0095] Typically, in the process according to the invention, the contact between the composite material and the gas comprising ozone lasts between 1 min and 8 h, in particular between 15 min and 6 h and, in particular, between 30 min and 4 h. More particularly, this contact can last, for example, on the order of 1 h (i.e. 1 h ± 15 min), on the order of 2 h (i.e. 2 h ± 15 min) or on the order of 3 h (i.e. 3 h ± 15 min).

[0096] The contact between the composite material and the ozone-containing gas in step c) is solvent-free. In other words, the composite material is not dispersed in a solution during step c). This step therefore consists of a gas / solid ozonation. In the process according to the invention, the contact between the composite material and the ozone-containing gas can be carried out in any system allowing a so-called "gas / solid" reaction, i.e., in an apparatus or device that efficiently brings a gas into contact with a solid. Considering the solid phase corresponding, in the process according to the invention, to the composite material, the contact can be discontinuous, semi-continuous, or continuous.

[0097] Everything described in International Application WO 2020 / 148497 A1 [1] concerning the process, devices and installations for bringing cyclodextrins and / or cyclodextrin derivatives into contact with ozone-containing gas, and in particular from page 10, line 3 to page 11, line 16, applies mutatis mutandis to the process, devices and installations for bringing the composite material into contact with ozone-containing gas in the context of the invention.

[0098] A person skilled in the art will be able to adapt, without inventive effort, the gas flow rate during contact between the composite material and the ozone-containing gas, according to the devices or installations chosen for this contact, and in particular the size of the reactor. The gas flow rate at the outlet of the ozone-containing gas source, and in particular at the outlet of the ozonator, can be constant or variable during step c). Typically, the gas flow rate at the outlet of the ozone-containing gas source, and in particular at the outlet of the ozonator, is between 10 NL / h and 1000 NL / h, in particular between 30 NL / h and 500 NL / h, and especially between 50 NL / h and 200 NL / h.

[0099] The process according to the invention may include an additional step following step c) of recovering the inorganic solid support loaded with cyclodextrins and / or ozonated cyclodextrin derivatives after their contact with the ozone-containing gas. This recovery may consist of unloading the solid support loaded with cyclodextrins and / or cyclodextrin derivatives from the reactor as previously defined in which the contact took place.

[0100] The oxidizing composite material according to the invention, i.e. corresponding to the inorganic solid support loaded with cyclodextrins and / or ozonated cyclodextrin derivatives, can be stored at a temperature between -80°C and 50°C, in particular between -80°C and 40°C and, in particular, between -25°C and -15°C, under vacuum, ambient air, humid air, dry air, carbon dioxide, inert gas such as argon, nitrogen or a mixture thereof.

[0101] The present invention also relates to the use of an oxidizing composite material as defined above, or of the ozonated cyclodextrins and / or cyclodextrin derivatives it contains, as a disinfectant (in particular for eliminating biological agents as defined below), depolluting agent, cleaner, or biocide (in particular fungicide, bactericide, insecticide, or herbicide). The activity of the oxidizing composite material according to the invention as a disinfectant, depolluting agent, cleaner, or biocide is due to the oxidizing power of this material, and in particular to the oxidizing power of the ozonated cyclodextrins and / or cyclodextrin derivatives it contains, and / or of the free molecules that may be created following the ozonation of the cyclodextrins and cyclodextrin derivatives.

[0102] In other words, the present invention relates to a method for disinfecting, decontaminating or cleaning a fluid, a material or a surface, organic or inorganic, consisting of bringing this fluid or this surface into contact with an oxidizing composite material as previously defined or with ozonated cyclodextrins and / or cyclodextrin derivatives that it contains and in particular with a liquid in which such an oxidizing composite material has been brought into contact and in which the ozonated cyclodextrins and / or cyclodextrin derivatives have dissolved forming a liquid having oxidizing properties.

[0103] For the purposes of this invention, "disinfecting, decontaminating, or cleaning a fluid, material, or surface" means reducing the quantity or activity of biological agents or chemical compounds present in the fluid or on the surface before contact with the oxidizing composite material according to the invention and / or with the ozonated cyclodextrins and / or cyclodextrin derivatives obtained from this composite material. This reduction in quantity may involve the elimination or destruction of these agents or compounds and / or their transformation into less harmful elements.

[0104] Any fluid susceptible to contamination by one or more biological agents or one or more chemical compounds can be subjected to a disinfection, decontamination, or cleaning process according to the present invention. The term "fluid" includes both gases and liquids.More specifically, such a fluid can be chosen from ambient air or the gaseous atmosphere of a site such as a domestic room, a cold storage room, or an industrial confined space; municipal water, river water, well water, groundwater, pond water, lake water, swimming pool water, aquarium water, water used for cooling air conditioning systems or cooling towers; a sample taken from a chemical reactor; domestic wastewater; a product, particularly a liquid, an effluent, or wastewater originating from intensive livestock farms or from industries or facilities in the chemical, pharmaceutical, cosmetic, agricultural, food processing, maritime, aeronautical, or space sectors; or a mixture thereof. It should be noted that, when the fluid is ambient air or a gaseous atmosphere, the oxidizing composite material as previously defined allows for its treatment by depolluting, disinfecting, and / or eliminating odors.Any surface susceptible to contamination by one or more biological agents and / or one or more chemical compounds can be subjected to a disinfection, decontamination, or cleaning process according to the present invention. Advantageously, within the scope of the present invention, the surface to be disinfected, decontaminated, or cleaned can be a textile, an inorganic surface, and in particular a metal surface such as aluminum, metal alloys, steel, and in particular stainless steel, tinplate, silicon, glass generally containing silicates, silica glass, ceramics, brick, porcelain, cement, concrete, asphalt, stone, granite, plastic, textiles, or any combination thereof.More specifically, such a surface can be chosen from large installations such as an industrial object like an electronic device or a machine used in the food industry, a vehicle, a carcass, an aircraft, a tank, a restaurant kitchen, a cold storage room, a sanitary facility, a container, a part of a dwelling such as a roof, a facade, a terrace, a driveway; and small installations such as systems embedded in space, in ships or submarines, medical devices or pipes, and textile elements such as clothing or coverings. It can also be an organic surface such as soil or earth, wood, or a vegetated surface.For the purposes of this invention, "plant surface" means a plant, a fungus or a moss, a part of a plant such as leaves, stems, roots, fruits or seeds, a part of a fungus such as the sporophore or mycelium, or a group of plants or fungi.

[0105] The term "biological agent" encompasses natural microorganisms such as bacteria, archaea, parasites, protozoa, fungi, yeasts, and viruses; toxins produced by such microorganisms or by other organisms; protein-based pathogens like prions; and genetically modified microorganisms. These biological agents can exist as aggregates of multiple microorganisms or as multicellular communities, such as biofilms.

[0106] In light of the above, it is clear that plants or parts of plants can, in certain applications, be the surface to be treated. In this case, the oxidizing composite material as previously defined, or the ozonated cyclodextrins and / or cyclodextrin derivatives obtained from this oxidizing composite material, serve to eliminate microorganisms such as fungi or bacteria present on these plants or parts of plants. In other applications, the plants or parts of plants constitute the biological agent to be eliminated, and the composite material as previously defined, or the ozonated cyclodextrins and / or cyclodextrin derivatives obtained from this oxidizing composite material, becomes a herbicidal agent.A person skilled in the art will be able to determine, without inventive effort and if necessary with the help of routine tests, the quantity of oxidizing composite material or of ozonated cyclodextrins and / or cyclodextrin derivatives to be used according to the intended application.

[0107] By "chemical compound" we mean an unwanted compound such as a pollutant or contaminant that may be present or is present in a fluid or material or on a surface.By way of illustrative and non-limiting examples, the compound may be chosen from among a volatile organic compound, nitrogen dioxide (NO2), carbon monoxide (CO), sulfur dioxide (SO2), acrolein, a phenol, an insecticide, a pesticide, a sulfur compound such as hydrogen sulfide (H2S), a thiol or a mercaptan, a saturated or unsaturated hydrocarbon such as an alkene like ethylene or a polycyclic aromatic hydrocarbon, a volatile organic compound such as an aldehyde, formaldehyde, acetaldehyde, naphthalene, a primary amine, particularly an aromatic one, indole, skatole, tryptophan, urobilinogen, pyrrole, benzene, ethylbenzene, toluene, a xylene, styrene, naphthalene, a halogenated compound, a toxin, a carbohydrate, a peptide, a protein, a glycoprotein, a pharmaceutical compound, a pharmaceutical derivative, or a mixture thereof.

[0108] The contact between the fluid, the material or surface, and the oxidizing composite material according to the invention can be achieved in various ways, particularly depending on whether the fluid is gaseous or liquid. Thus, the oxidizing composite material can be introduced into the liquid fluid, deposited or applied to the surface, placed in contact with the gaseous material or fluid (static exposures), or the fluid, particularly a gaseous fluid, can be circulated over the oxidizing composite material (dynamic exposure). Alternatively, as previously mentioned, it is possible to use ozonated cyclodextrins and / or cyclodextrin derivatives obtained from this oxidizing composite material after their dissolution in a solution and, optionally, after their separation from the solid, inorganic, and porous support.

[0109] In some of these variants, it may be advantageous to condition the oxidizing composite material according to the invention, in particular in the form of a column in which the material according to the invention corresponds to a fixed bed (immobile particles) or to a fluidized bed whose liquid or gaseous fluid ensures the fluidization.

[0110] In the case where the oxidizing composite material according to the invention is applied to a surface, this application can be done by sprinkling the oxidizing composite material or by spraying a solution, dispersion, emulsion, micro-emulsion, nano-emulsion or suspension or colloidal suspension containing the oxidizing composite material and therefore the dissolved ozonated cyclodextrins and / or cyclodextrin derivatives.

[0111] In cases where the oxidizing composite material is introduced into the liquid fluid, it may be advantageous to stir the resulting mixture.

[0112] The present invention also relates to the use of an oxidizing composite material as previously defined or of ozonated cyclodextrins and / or cyclodextrin derivatives contained therein to increase the shelf life of fruits and vegetables.

[0113] Indeed, it is possible to significantly increase the shelf life of fruits and vegetables when the oxidizing composite material as defined above, or the ozonated cyclodextrins and / or cyclodextrin derivatives it contains, are placed next to the fruits and vegetables without direct contact. For example, the oxidizing composite material according to the invention can be placed in a first open container such as a small dish, and this first container, along with the fruits and / or vegetables whose shelf life is to be extended, can be placed in a second closed container such as a box.

[0114] The present invention also relates to an oxidizing composite material as previously defined, or to the ozonated cyclodextrins and / or cyclodextrin derivatives it contains, for use as a medicinal product. Indeed, due to the biocidal properties of this material, and in particular the biocidal properties of the ozonated cyclodextrins and / or cyclodextrin derivatives it contains, it can be considered for the treatment or prevention of diseases or disorders caused by a microorganism as previously defined. In particular, these diseases or disorders are cutaneous diseases or disorders. Illustrative examples of such diseases or disorders include impetigo, lymphangitis, boils, abscesses, anthrax, fungal infections, warts, eczema, seborrheic dermatitis, shingles, and herpes. The term "medicinal product" includes both human and veterinary medicinal products.

[0115] The present invention also relates to the use of an oxidizing composite material as previously defined, or the ozonated cyclodextrins and / or cyclodextrin derivatives it contains, as a chemical reagent. Indeed, this material can be used as an oxidizing agent in a chemical reaction.

[0116] Other features and advantages of the present invention will become apparent to those skilled in the art upon reading the examples given below, which are provided by way of illustration and not limitation, with reference to the accompanying figures. BRIEF DESCRIPTION OF THE FIGURES

[0117] Figure 1 shows the percentage loss of oxidizing power of an oxidizing composite material according to the invention as a function of time and storage conditions (freezer or room temperature).

[0118] Figure 2 shows the most characteristic signals of the NMR spectrum 1H of an oxidizing composite material according to the invention placed in DMF-d7 at -70°C.

[0119] Figure 3 shows the number of viable Colletotrichum musae spores as a function of different HPbCD / Si and Oz-HPbCD / Si concentrations for two replicates (3 Petri dishes per replicate). The positive control was performed in the absence of composite material.

[0120] DETAILED DESCRIPTION OF SPECIFIC IMPLEMENTATION METHODS

[0121] Example 1: Oxidizing material of the silica-cyclodextrin type ozonated composite.

[0122] I. Preparation of the silica-cyclodextrin composite.

[0123] 1.1. Reagents used.

[0124] The porous inorganic support is in the form of porous and spherical silica particles (Siliasphere® SS300A, supplier SILICYCLE).

[0125] (2-Hydroxypropyl)-P-cyclodextrin (HPbCD) (lot #BCCC1925, purity > 94%, MS = 0.9, produced by Wacker Chemie AG, Burghausen, Germany) was purchased from Sigma-Aldrich and is used without further purification.

[0126] 1.2. Preliminary remarks and preparatory work.

[0127] The method for manufacturing porous silica particles containing solid HPbCD (i.e., silica-HPbCD or Si-HPbCD composites) comprises two successive steps: impregnation and drying. The impregnation step consists of contacting the porous substrate with a solution containing HPbCD to fill the pores with this solution. The drying step of the impregnated particles consists of evaporating the solvent from the solution to retain and, in particular, crystallize the HPbCD within the substrate's pores.

[0128] To study the effect of the impregnation solution concentration on the composite properties, three different aqueous solutions of HPbCD (i.e., 100, 300, and 500 gL) were used. 1 HPbCD) were used. The maximum concentration tested was chosen taking into account the solubility of HPbCD in water, which is greater than 500 g / L 1 at room temperature.

[0129] The density and viscosity of the different impregnation solutions were measured experimentally, and the values ​​obtained are shown in Table 1. Table 1: Density and viscosity of water / HPbCD solutions at 20°C

[0130] As expected, the density and viscosity of the HPbCD solution increase with concentration. Note that, at the highest concentration, the viscosity is approximately 20 times that of water at the same temperature. It is known that the physical parameters of impregnation solutions, namely density and viscosity, can play a role in the impregnation process, particularly viscosity, since the lower the viscosity of the impregnation solution, the faster the impregnation.

[0131] The porous silica particles were purified before use at 110°C for 24 h. The mass loss during this step was always less than 0.1% by weight, in accordance with the supplier's data (specification of volatile matter content at 160°C < 2%, observed value of 0.1% by humidity measurements).

[0132] 1.3. Impregnation stage.

[0133] The method used is a "non-standard" protocol of the pore volume impregnation (PVI) method. Indeed, it was chosen to use only a fraction of the pore volume, and not the exact value determined from gas and mercury porosimetry experiments.

[0134] The motivations for this choice are as follows: (i) to localize the impregnation solution only in the pores of the support during the impregnation step by limiting as much as possible the presence of liquid on the surface of the particles; (ii) as there is some uncertainty in determining exactly this pore volume, to be sure that the volume used of the impregnation solution is strictly less than the pore volume of the support.

[0135] Since the impregnation rate of the particles, corresponding to the mass percentage of HPbCD per mass of Si-HPbCD composite, is directly proportional to the amount of impregnation solution present in the porous particle, it was chosen to saturate between 80% and 95% of the porous volume with the impregnation solution. This safety margin (5% to 20% of the porous volume) was deemed sufficient to prevent HPbCD from forming and, in particular, from crystallizing on the particle surface after drying.

[0136] The protocol used was as follows: a glass flask was filled with a precise mass (approximately 10 g) of dry SS300A. The total mass of the flask containing the silica was recorded to perform a mass balance after the final drying step, in order to calculate the impregnation rate. In these experiments, a volume of impregnation solution equal to 84% of the porous volume of the silica was used.

[0137] Using the experimental value for the pore volume of the silica support (i.e., 1.2 ml per gram of silica), the volume of the impregnation solution was calculated. Based on the density of the chosen impregnation solution (see Table 1), the corresponding mass of solution was precisely determined and added to the silica particles using a glass Pasteur pipette on a precision balance.

[0138] At the end of this step, a cake of wet particles was obtained because the liquid solution had not (at that moment) completely penetrated the pores of the silica, and liquid bridges formed by capillary action between the solid particles.

[0139] The cake of moist particles was stirred by hand for a few minutes using a spatula, then the flask was sealed with a stopper. The flask was sonicated for an initial period of 15 minutes, then stirred by hand for a few seconds, and sonicated again for 15 minutes.

[0140] This step in the protocol is very effective in finalizing the incorporation of the impregnation solution into the pores of the silica support. After sonication, no apparent trace of liquid solution is visible to the naked eye in the flask (and no capillary bridges are present between the particles). Indeed, at the end of sonication, the impregnated particles can be handled very easily (free flow of particles, no sticking, no more liquid capillary bridges, no water droplets).

[0141] 1.4. Drying stage.

[0142] Oven drying

[0143] For the oven drying step, the particles were placed in an oven at a constant temperature (110°C, 70°C, or 50°C). The masses of the samples were carefully monitored during drying. This drying step was considered complete when the mass change was less than 1%. Depending on the oven temperature, the particles were dried for 24 h at 110°C, 48 h at 70°C, and 96 h at 50°C. Finally, the composite particles were stored in a sealed container until use. For each drying condition, an experiment was repeated to test reproducibility.

[0144] Mass balances before and after drying of the different composites lead to the conclusion that the impregnation rate of the composites does not depend on the drying temperature (i.e., the same mass of CD is deposited in the particle regardless of the drying temperature). The morphology of these composites, studied by scanning electron microscopy, and all measured values, such as average pore size, pore volume, specific surface area, and actual density, for particles dried at 50°C and 70°C, are identical to those obtained for particles dried at 110°C. In conclusion, under these conditions, the drying temperature of the particles has no influence on the physical characteristics of the composites.

[0145] Freeze-drying

[0146] As an alternative to oven drying, freeze-drying can be used. The equipment used for this method is an Alpha 3-4 LSCbasic freeze dryer (CHRIST). It is equipped with a manifold and several valves, allowing for the simultaneous drying of different samples.

[0147] The vials containing the porous silica support impregnated with the CD solution are capped and placed in a freezer at -25°C for a minimum of one night to ensure that all the solvent is frozen.

[0148] The freeze dryer is switched on and brought to operating conditions (e.g., T = -111.8°C, P > 1 mbar). When the freeze-drying conditions are reached in approximately 20 minutes, the vial containing the frozen impregnated porous support is placed in a freeze-drying container and fitted onto one of the (previously closed) taps of the manifold.

[0149] The tap is then opened, the sample is connected to the freeze dryer, and the primary and secondary drying phases of the sample take place to achieve minimal residual moisture. By selecting the equipment to perform the drying cycles in infinite mode, the transition from one cycle to the other occurs automatically.

[0150] When freeze-drying is complete, after approximately 20–24 hours (T ~ -105–110°C, P ~ 0.1 mbar), the manifold valve is closed and the sample can be retrieved. The dry composite is weighed, and the water loss before freezing / after freeze-drying, as well as the impregnation rate (mass % of organic product), is calculated.

[0151] 1.5. Characterization of the Si-HPbCD composite.

[0152] To establish a quantitative comparison between the particles before (i.e., SS300A) and after impregnation with a 300 g / L HPbCD solution and drying in an oven for 24 h at 110°C (i.e., Si-HPbCD composites), we first examined the particle morphology studied by SEM (Scanning Electron Microscopy). The Si-HPbCD composites exhibit characteristics very similar to those of SS300A: most particles are spherical, with a few small inclusions and defects visible on the surface of some particles. No significant crusting, HPbCD deposition, or massive particle clumps or aggregates were observed. Particle size analysis revealed very similar cumulative particle size distributions, again confirming that the particles did not increase in diameter, meaning that no significant HPbCD crusting is present on the particle surface.Therefore, no significant difference can be noted between the particles before and after impregnation / drying.

[0153] From all the characterization analyses performed on 4 composites with different impregnation levels (two identical experiments were carried out to assess reproducibility) and compared to SS300A, it can be concluded that: (i) the composite manufacturing protocols give highly reproducible results; (ii) the methods used for characterization are robust and reliable (corroborated results); (iii) since no HPbCD deposits were observed (or measured) on the surface of the composite particles, the HPbCD is therefore necessarily contained within the porosity of the porous support; (vi) the crystallization of HPbCD inside the pores does not induce the creation of closed (hidden) porosity; (v) the composites have pores filled (totally or partially) with HPbCD and pores that are completely empty;(vi) as no shift in the pore size distribution was measured for the composites towards smaller pore sizes, the pores are filled but not lined (i.e. the internal surface of the pores is not covered with HPbCD); (vii) the largest pores appear to be preferentially filled.

[0154] II. Preparation of the ozonated Si-HPbCD composite.

[0155] The reactor is first loaded with the Si-HPbCD composite directly onto a balance with an accuracy of ±0.005 g. Approximately 3 g of the Si-HPbCD composite, with an impregnation percentage (i.e., the mass percentage of HPbCD in the composite) of 22%, is used. The reactor is then closed, the temperature probe connected to the monitoring system, the reactor mounted on the bench, and the cooling pipes connected to the reactor's double jacket. Before starting the synthesis, a 5-minute leak test is always performed with nitrogen at 2 bar to ensure that all components of the bench are perfectly sealed. All processing lines are ventilated with pure oxygen, and the reactor, regulated to a temperature (Tr) of 25°C, is first isolated to initiate ozone production.The pressure drop is adjusted in the bypass line to equalize the pressure drop in the reactor to avoid any change in the gas flow rate when this line is closed to send the gas into the reactor.

[0156] The gas flow rate (Qf) and the ozone concentration (CO3) are then set to the correct values, namely a Qf of 100 NL / h and a CO3 of 100 g / Nm³ 3 and stabilized using the reactor bypass line before the start of synthesis. When all process parameters are perfectly stable, the O2 / O3 gas mixture from the ozone generator is sent to the reactor by turning the valves to close the bypass line. The synthesis time t = 0 is defined at this point.

[0157] Contact between the ozone and the Si-HPbCD powder is maintained for a specific reaction time (denoted tr) of 2 h. At the end of the synthesis, the ozone concentration is gradually reduced to zero, and then the ozone generator is switched off. The reactor is then purged with pure oxygen, followed by nitrogen, before being removed from the bench and transferred to a glove box (under air) for safe opening. The ozonated Si-HPbCD composites are then discharged from the reactor into a glass vial using a funnel and sealed with a stopper. The product is immediately sampled for analysis. Finally, the vial is hermetically sealed and stored in a freezer at -20°C.

[0158] III. Physicochemical properties of the ozonated Si-HPbCD composite.

[0159] 111.1. Oxidizing power.

[0160] The total oxidation capacity, called oxidizing power (OP), of the solid materials obtained from the synthesis is determined by iodometric titration carried out according to the following procedure: 20 mL of a 0.1 mol / L aqueous solution of potassium iodide (Kl) 1 are stirred in a 125 mL Erlenmeyer flask; then, the pH of the solution is adjusted to approximately 2 with a few drops of sulfuric acid (1 mol / L) 1 ); finally, a precise quantity of ozonated Si-HPbCD composite of 0.05-0.1 g measured to ± 10' 4 g, is added to the acidified Kl solution. The reagents are kept in contact under stirring for 60 min before titration.

[0161] The iodometric titration method is based on the following principle: upon contact with oxidizing agents, iodide ions (I₂) are oxidized to diiodine (I₂), coloring the initially transparent solution brown / orange. The amount of hydrogen peroxide (H₂O) generated is easily obtained by volumetric titration using a sodium thiosulfate solution with a concentration of 2 × 10⁻³ -3 ± 5.10' 5 mol.L 1 .

[0162] The oxidizing power of the material is therefore directly proportional to the amount of iodine generated. The PO is expressed here as the ratio of the mass of iodine produced to either the mass of the ozonated Si-HPbCD composite or to the mass of HPbCD.

[0163] Table 2 below presents the oxidizing power obtained for the ozonated Si-HPbCD composite under the conditions described above and compared to the oxidizing power obtained for ozonated HPbCD alone under comparable conditions (HPbCDref). In Table 1, "POP" represents the Oxidizing Power of the Product expressed in mg of diiodine / g of product, "POCD" the Oxidizing Power of Cyclodextrin expressed in mg of diiodine / g of cyclodextrin, and "POCDREF" the Oxidizing Power of the reference Cyclodextrin, i.e., HPbCDref.

[0164] Table 2:

[0165] The oxidizing power of the ozonated Si-HPbCD composite material expressed per g of HPbCD is almost 11 times higher than the oxidizing power of the so-called reference ozonated HPbCD i.e. unsupported.

[0166] 111.2. Stability of oxidizing power.

[0167] The stability of the ozonated Si-HPbCD composite material (evolution of oxidizing power as a function of time) was evaluated for 30 days at two temperatures, namely -19°C ± 2°C, with the composite material placed in a freezer, and 21°C ± 2°C, with the composite material left at room temperature.

[0168] A 2 g mass of ozonated Si-HPbCD composite material was divided into 0.1 g portions placed in airtight vials and stored in a freezer or at room temperature. The oxidizing power was determined by the iodometric method as explained in section lll.l above.

[0169] The decrease in the material's oxidizing properties during storage time (ts) is quantified by the rate at which oxidizing power is lost (denoted OPioss). This indicator quantifies the stability of the PO over time: the lower the OPioss, the more stable the product's oxidative properties are over time. The PO loss (in %) is defined as the difference in PO between the initial PO (measured at ts = 0) and the PO measured at storage time ts, normalized by the initial PO obtained at ts = 0.

[0170] The results are shown in Figure 1. The evolution of oxidizing power over time shows that the product retains its oxidative properties well when stored at -19°C ± 2°C. A loss of only 14% of the PO is measured after 30 days if the product is stored in a freezer, compared to 81% at room temperature.

[0171] These results are identical to those obtained with the unsupported product (ozonated HPbCD crystals), as the measured PO loss rate was 15% for freezer storage, compared to 76% at room temperature. The stability study of the unsupported product on the silica matrix was conducted over 65 days, with a measured PO loss rate of 18% at -20°C. It can therefore be assumed that the supported product, which behaves identically during the first 30 days of storage, could be stored for up to two and a half months in a freezer while retaining at least 80% of its oxidizing properties.

[0172] 111.3. Characterization by nuclear magnetic resonance (NMR).

[0173] Figure 2 shows the NMR spectrum 1H in DMF-d7 at -70°C is typical of an oxidizing composite material according to the invention (ozonated Si-HPbCD). The signal assignment presented was obtained by conducting a thorough NMR study based on experiments. 1 H / 13 C in one and two dimensions and on the use of reference products.

[0174] From these results, it is possible to quantify the free species contained in the ozonated Si-HPbCD composite (Table 3) and in the HPbCDref (Table 5) as well as the species grafted onto the HPbCD of the ozonated Si-HPbCD composite (Table 4) and onto the HPbCDref (Table 6).

[0175] Table 3: Assay of free species contained in the ozonated Si-HPbCD composite

[0176] Table 4: Assay of species grafted onto the HPbCD of the ozonated Si-HPbCD composite

[0177] Table 5: Assay of free species contained in HPbCDref

[0178] Table 6: Dosage of species grafted onto HPbCDref

[0179] These various studies show that the degradation rate of the hydroxypropyl (HP) groups in HPbCD is much higher (>90%) than with HPbCDref crystals used as is (<10%), demonstrating that the HPbCD contained in the composite reacts almost completely. The initial HPbCD is partially degraded (bond cleavage) but retains its overall lampshade structure. This result was subsequently confirmed by small-angle and wide-angle X-ray scattering (SAXS / WAXS) measurements.

[0180] Furthermore, the so-called "free" products are mobile species that are likely present in the HPbCD cavity. Their transfer into the solvent can vary depending on their complexation equilibrium constant. 111.4. Evaluation of the fungicidal activity of the oxidizing composite material according to the invention.

[0181] The antifungal effect of the ozonated Si-HPbCD composite (“Oz-HPbCD / Si”) was tested on the fungal strain Colletotrichum musae, responsible for banana anthracnose. The same experiment was performed with the non-ozonated Si-HPbCD composite (“HPbCD / Si”) and HPbCDref. In this experiment, an identical methodology was followed with two concentrations of ozonated composites: 29.7 g composite-L 1 (corresponding to 6.8 gHpbCDref. L' 1 ) and 2.97 g composite-L' 1 (corresponding to 0.68 gHpbCDref.L' 1). The results of the viable counts according to the different concentrations of HPbCD / Si and Oz-HPbCD / Si (for two replicates) are reported in Figure 3.

[0182] The positive control showed normal fungal growth with complete proliferation on Petri dishes. Interestingly, the HPbCD / Si composite (i.e., the non-ozonated product) had the greatest effect on inhibiting the fungal strain. Indeed, with the HPbCD / Si composite used at 6.8 gHPbCD.L' 1 83% inhibition of the fungal strain was achieved compared to the positive control. Therefore, it can be concluded that non-ozonated HPbCD had a significant influence on the development of this Colletotrichum musae strain.

[0183] HPbCD / Si exhibited antifungal activity at all concentrations, a finding also observed with unsupported HPbCD. One hypothesis that may explain this inhibition of fungal growth with the addition of HPbCD alone is osmotic imbalance, leading to water diffusion across the membrane in response to osmotic pressure caused by an imbalance of molecules on either side of the membrane. The crucial process leading to cell death is the permeabilization of plasma membranes. Sugar-rich environments pose a significant challenge to microorganisms, and in some cases, the resulting osmotic and molecular imbalances can severely limit microbial metabolism and growth. We formulated this hypothesis based on the strong inhibition observed with the addition of CD alone (either HPbCD or the HPbCD / Si composite).

[0184] However, the results in Figure 3 show that the use of Oz-HPbCD / Si is necessary to achieve better inhibition of fungal strain growth. Thus, antifungal activity is almost complete with Oz-HPbCD / Si at 29.7 g / L composite. 1 corresponding to a concentration of 6.8 g H pbCDref.L -1 In comparison, the antifungal activity of unsupported Oz-HPbCD begins to be effective at 59.4 g / L 1 However, the inhibition remains partial and never reaches total limitation. Therefore, with the ozonated composite, the concentration of CD used is reduced by 89%. Consequently, the fungal efficacy is ten times greater, leading to the use of a much smaller quantity of HPbCD to achieve the same effects. This is an interesting result that proves that supported HPbCD can contribute significantly to cost reduction and avoid production losses.

[0185] Example 2: Oxidizing material of the silica-glucose composite type ozonated.

[0186] I. Preparation of the silica-hydroxypropylcellulose (Si-HPC) composite.

[0187] 1.1. Products used.

[0188] The porous inorganic support is a non-spherical silica SI Ll FLASH SF300A (supplier SILICYCLE).

[0189] The carbohydrate used is a hydroxypropylcellulose (HPC) obtained from Accros- Organics, PM ~ 100,000. CAS# = 9004-64-2.

[0190] 1.2. Protocol.

[0191] - Drying stage of the porous support

[0192] 5.0066 g of SF300A were placed in an oven at 110°C for 5 hours in a glass flask. The mass loss was 4.17%, consistent with the moisture content of these particles.

[0193] - Impregnation stage:

[0194] Two aqueous HPC solutions (impregnation solutions) were prepared: one at 100 g / L and one at 50 g / L. Note that aqueous HPC solutions are relatively viscous.

[0195] A given mass of dried beads is placed in a pre-weighed flask. A precise mass of impregnation solution is then introduced over the beads using a Pasteur pipette. The mass of solution is calculated so that the volume of impregnation solution is equal to 90% of the porous volume of the particles.

[0196] The impregnated beads are stirred with a spatula, then the bottle is closed and placed under ultrasound for 10 minutes, stirred manually, then placed back under ultrasound for 10 minutes (to better penetrate the solution into the pores).

[0197] - Drying stage

[0198] The bottle is opened and placed in an oven at 110°C for a minimum of 24 hours. The solvent in the impregnation solution (water in our case) evaporates, and the organic product of interest (HPC here) crystallizes within the porous particle, ultimately forming the "composite." 1.3. Characterization of the Si-HPC composite.

[0199] The composite is then weighed and the impregnation rate (mass % of organic product) is calculated.

[0200] The density and viscosity of these solutions were measured at a temperature of 20°C.

[0201] The results are given in Table 7.

[0202] Table 7: Density and viscosity of water / HPC solutions at 20°C

[0203] For comparison, the viscosity at 20°C of a 100 g / L HPbCD solution is 0.00388 Pa·s, which is approximately 64 times lower than that of an HPC solution at the same concentration. The viscosity at 20°C of a 500 g / L HPbCD solution is 0.02019 Pa·s, which is approximately 13 times lower than the viscosity of the 50 g / L HPC solution.

[0204] The SF300 / HPC composite obtained using a 50 g / L HPC solution has an impregnation rate of 3.7% and is a powder with relatively homogeneous particle sizes that flows well. In contrast, the Si-HPC composite obtained using a 100 g / L HPC solution has an impregnation rate of 6.6% and is a powder with non-homogeneous particle sizes, including large lumps and agglomerates. The powder flows well, but the particle size distribution is not uniform.

[0205] The resulting impregnation rate is low because it is directly proportional to the concentration of the solution used, which must be low in HPC to avoid excessive viscosity. If the HPC concentration in the solution is low, the amount of HPC crystallized within the particle is also low.

[0206] The most homogeneous composite in terms of particle size, i.e. the composite containing 3.7% HPC, obtained with the 50 g / L HPC solution, is therefore chosen to carry out the reaction tests under ozone.

[0207] II. Preparation of the ozonated silica-HPC composite.

[0208] The ozonation protocol is identical to that explained for cyclodextrins.

[0209] Here, a 2 g mass of silica-HPC composite with 3.7% HPC is loaded into the reactor. After a nitrogen leak test and a purge under pure O2, the reactor is isolated and temperature-controlled at 25°C. The ozone (O3) concentration in the feed gas is adjusted between 90 and 110 g / Nm³ 3 and the flow rate between 90 and 110 NL / min. When all process parameters are stable, the O2 / O3 mixture is sent to the reactor containing the composite. The reactor is maintained under an ozone flow for two hours at a constant temperature and gas flow rate. Once the reaction time has elapsed (2 h in this case), the ozone concentration is reduced to zero and the reactor is purged with pure oxygen, then with nitrogen. The product is then packaged in a hermetically sealed glass bottle. The product is analyzed and then stored in a freezer at a temperature between -20°C and -25°C.

[0210] Note that the reaction between ozone and the Si-HPC composite is exothermic (the same behavior as with a composite containing HPbCD). For example, during the experiment, a temperature rise of 2.5°C to 3°C was observed in the reactor at t = 0 under these conditions.

[0211] III. Oxidizing power of the ozonated Si-HPC composite.

[0212] An oxidizing power test was carried out at the end of the synthesis on the product obtained.

[0213] In an Erlenmeyer flask, 20 mL of 0.1 mol / L potassium iodide solution and two drops of concentrated sulfuric acid are introduced. A mass of powder is weighed and then added to the solution while stirring, rinsing the container with 20 mL of distilled water.

[0214] Upon immediate contact with the ozonated powder, the Kl solution turns yellow / orange, indicating that the iodide has oxidized to iodine through reaction with the ozonated composite. The test is repeated three times to calculate a representative average value of oxidizing power.

[0215] After two hours of reaction, the amount of diiodine formed in each of the 3 Erlenmeyer flasks is determined by volumetric titration with a 2 x 10 sodium thiosulfate solution. -3 mol / L.

[0216] The average oxidizing power of the ozonated Si-HPC composite is:

[0217] - POP = 22 ± 2 mg h per gram of product

[0218] - POHPC = 583 ± 38 mg h per gram of HPC

[0219] The low POP value (per gram of composite) is due to the composite's low HPC content (only 3.7% by mass). However, the HPC in the composite reacts very well, as evidenced by its high oxidizing power per gram of HPC.

[0220] References

[0221] [1] International application WO 2020 / 148497 Al.

[0222] [2] International application WO 2022 / 013504 Al.

Claims

38 DEMANDS 1. Oxidizing composite material comprising a solid, inorganic, porous support, all or part of whose pores contain cyclodextrins and / or cyclodextrin derivatives rendered oxidizing by ozone treatment.

2. Oxidizing composite material according to claim 1, characterized in that said solid, inorganic and porous support essentially comprises mesopores.

3. Oxidizing composite material according to claim 1 or 2, characterized in that said solid, inorganic and porous support is in the form of objects whose average size is between 1 pm and 1 mm, in particular between 15 pm and 800 pm and, in particular, 20 pm and 600 pm.

4. Oxidizing composite material according to any one of claims 1 to 3, characterized in that said solid, inorganic and porous support is based on (1) a porous metal or metal alloy; (2) a porous metal oxide; (3) a porous mixed metal oxide; (4) a mixture of porous metal oxides; or (5) a porous ceramic, said solid, inorganic and porous support being preferably made of silica.

5. Oxidizing composite material according to any one of claims 1 to 4, characterized in that said cyclodextrins and / or said cyclodextrin derivatives are selected from the group consisting of a-CD, P-CD, y-CD, hydroxypropyl a-CD, hydroxypropyl -CD, hydroxypropyl y-CD, dimethyl a-CD, dimethyl P-CD, dimethyl y-CD; sulfobutyl ether-a-CD, sulfobutyl ether-p-CD, sulfobutyl ether-y-CD, sulfated a-CD, sulfated P-CD, sulfated y-CD, phosphated a-CD, phosphated P-CD, phosphated y-CD; carboxymethylated a-CDs, carboxymethylated p-CDs, carboxymethylated y-CDs, carboxymethyl etherized a-CDs, carboxymethyl etherized p-CDs, carboxymethyl etherized y-CDs, 3-trimethylammonium-2-hydroxypropyl ether-a-CD; 3-trimethylammonium-2-hydroxypropyl ether-p-CD; 3-trimethylammonium-2-hydroxypropyl ether-y-CD; and mixtures thereof. 39 6. Oxidizing composite material according to any one of claims 1 to 5, characterized in that said cyclodextrins and / or said cyclodextrin derivatives rendered oxidizing by ozone treatment have been chemically modified by grafting or introduction of at least one oxidizing function following this treatment, said oxidizing functions being advantageously chosen from the group consisting of a percarbonic group (-C(=O)-O-OH), a hydroperoxide group (RO-OH), an organic peroxide group (R'-O-OR), a trioxide group (ROO-OH), a molozonide group, an ozonide group and a diperoxide group.

7. A process for preparing an oxidizing composite material according to any one of claims 1 to 6, said process comprising a) impregnating a solid, inorganic, porous support with a solution comprising cyclodextrins and / or cyclodextrin derivatives; b) drying the impregnated inorganic solid support obtained in step a), thereby obtaining a composite material consisting of an inorganic solid having all or part of its pores containing cyclodextrins and / or cyclodextrin derivatives; and then c) contacting the composite material obtained in step b) with a gas comprising ozone, thereby obtaining an oxidizing composite material.

8. A preparation process according to claim 7, characterized in that the impregnation technique used during said step a) is the pore volume impregnation (PVI) technique and in particular a pore volume impregnation technique employing a volume of said solution comprising cyclodextrins and / or cyclodextrin derivatives less than the pore volume of said solid, inorganic, porous support.

9. Preparation method according to claim 7 or 8, characterized in that said step a) comprises at least one manual stirring and / or at least one sonication.

10. Preparation process according to any one of claims 7 to 9, characterized in that said step b) consists of lyophilizing the solid support impregnated by the solution comprising cyclodextrins and / or cyclodextrin derivatives. 40 11. A preparation method according to any one of claims 7 to 10, characterized in that said gas comprising ozone at step c) is a gaseous mixture comprising ozone and at least one other gas such as dioxygen, carbon dioxide, dinitrogen or a mixture thereof.

12. Use of an oxidizing composite material according to any one of claims 1 to 6 or of the ozonated cyclodextrins and / or cyclodextrin derivatives it contains, as a disinfectant, depolluting, cleaning or biocidal agent.

13. Use of an oxidizing composite material according to any one of claims 1 to 6 or of the ozonated cyclodextrins and / or cyclodextrin derivatives contained therein, for disinfecting, decontaminating or cleaning a fluid, material or surface.

14. Use of an oxidizing composite material according to any one of claims 1 to 6 or of the ozonated cyclodextrins and / or cyclodextrin derivatives it contains, to increase the shelf life of fruits and vegetables.

15. Oxidizing composite material according to any one of claims 1 to 6 or ozonated cyclodextrins and / or cyclodextrin derivatives contained therein for use as a medicinal product.

16. Use of an oxidizing composite material according to any one of claims 1 to 6 or of the ozonated cyclodextrins and / or cyclodextrin derivatives it contains as a chemical reagent.

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