Method for capturing metals in an ingestible liquid

Abstract

The invention relates to a process for treating an ingestible liquid, preferably food-grade, consisting essentially of bringing said ingestible liquid into contact with a gel, said gel comprising at least one statistical polysaccharide of formula I having a weight-average molecular mass between 100kDa and 10000kDa: Formula I in which Rc is a group comprising a chelating agent, Z is a binder which may be a single bond or a hydrocarbon chain comprising between 1 and 12 carbon atoms, said chain being linear or branched, being able to comprise one or more unsaturations and being able to comprise one or more heteroatoms, preferably selected from nitrogen, oxygen, sulfur and atoms of the halogen family, x is between 0.005 and 0.6, y is between 0.05 and 0.5, the ratio y / x being greater than 0.2, and the sum x + y being greater than 0.1.

Description

Title of the invention: Method for capturing metals in an ingestible liquid Technical field

[0001] The present invention relates to the field of the treatment of ingestible liquids, in particular alcoholic beverages. More specifically, the present invention relates to the extraction of metals by a technological aid based on a chitosan carrying at least one chelating group. Prior art

[0002] Generally speaking, mineral elements are an integral part of ingestible liquids, such as alcoholic beverages.

[0003] In some cases, the presence of metal cations, particularly in excess, can be detrimental. For example, the presence of heavy metals such as lead and cadmium, for health reasons, should be avoided as much as possible. In the field of wines, in particular, trace metals of the transition metal type such as iron, manganese and copper can be detrimental. Indeed, beyond visible defects such as “ferric or copper casse” through the formation of troublesome precipitates, these metals can be involved in oxidation reactions that affect the stability of the wine (Nikolantonaki et al., revue des œnologues July 2022, pages 33-34; Tariba Biol. Trace Elem. Res. (2011) 144:143-156)

[0004] It is known that iron and copper are catalysts for oxidation reactions, particularly in the Fenton reaction where they act as a catalyst for the production of reactive oxygen species. They thus promote the degradation of wine during storage. To compensate for this low stability, winemakers may be led to add sulfites, stabilizing agents well known in the wine industry. However, these agents are controversial for their negative impact on the perception of wines among some consumers.

[0005] An alternative solution to improve the stability of a wine is the extraction of metal traces. Conventional metal chelators (Kreitman et al. J. Agric. Food Chem. 2013, 61,39, 9480-9487) have been studied and have shown an impact on oxidation, but their use is very complex as an exogenous additive. Furthermore, these chelators are dispersed and are part of the beverage intended for consumption because they are not extracted from the beverage before consumption.

[0006] The use of ion exchange resins has also been proposed for sweet wines (Tamasi et al. Molecules 2018, 23, 2873). Although it has been shown to be effective in reducing opalescence and tartrate deposits, observable at high concentrations, This solution is not suitable for reducing concentrations to lower values, which are also critical for oxidative stability. In addition, this solution has an impact on the color index of around 15%, involves significant handling of the wine, and has a direct effect on aromas and organoleptic quality. While an effect has been demonstrated for zinc, manganese, copper, and a major mineral element such as calcium, no effect has been demonstrated for lower metal traces (heavy metals, iron). Thus, these resins are suitable for smoothing high concentrations of metal cations, but not for specifically extracting critical metal traces. In addition, the large surface area of ​​such a resin has an organoleptic impact with the simultaneous depletion by chemisorption of less hydrophilic aromatic molecules.

[0007] Biopolymers such as chitosan can also be used. Thanks to their amine functions, such biopolymers can in fact chelate certain metals. The International Organisation of Vine and Wine (OIV) authorises the use of chitosan in the preventive treatment of ferric and copper casses in musts and wines at a maximum dose of 100 g / hl, with usual doses varying from 10 to 50 g / hl.

[0008] However, even if this solution remains interesting for limiting precipitation, this capacity to chelate decreases sharply under conditions of partly alcoholic solvent as well as at acid pH.

[0009] There is therefore a need to develop a solution making it possible to extract metals present in a food liquid in concentrations of the order of traces while limiting as much as possible the interactions with the other molecules of the food liquid, in particular when it comes to wine, in particular in alcoholic and / or acidic conditions. Summary

[0010] In order to meet this need, a method is proposed for treating an ingestible liquid, preferably food, consisting essentially of bringing said ingestible liquid into contact with a gel, said gel comprising at least one random polysaccharide of formula I having a weight-average molecular mass of between 100 kDa and 1000 kDa: Formula I in which Rc is a group comprising a chelating agent, Z is a binder which may be a single bond or a hydrocarbon chain comprising between 1 and 12 carbon atoms, said chain being able to be linear or branched, being able to comprise one or more unsaturations and being able to comprise one or more heteroatoms, preferably chosen from nitrogen, oxygen, sulfur and atoms of the halogen family, x is between 0.005 and 0.6, y is between 0.05 and 0.5, the ratio y / x being greater than 0.2, and the sum x + y being greater than 0.1.

[0011] According to a second aspect, a method of manufacturing an ingestible liquid, preferably food liquid, is proposed, characterized in that it integrates in one or more of its steps, the treatment specific to the method of treating an ingestible liquid mentioned above.

[0012] According to a third aspect, a technological aid is proposed for implementing the method for treating an ingestible liquid mentioned above, characterized in that it comprises at least one body in compact (e.g. pellets, beads, blocks) or particulate (e.g. powder) form of a gel as defined above.

[0013] According to a fourth aspect, there is provided a composition for treating an ingestible liquid, preferably food, characterized in that it contains the technological auxiliary described above and at least one other agent for treating or adjuvanting the ingestible liquid.

[0014] According to a fifth aspect, a device is proposed for bringing the technological aid described above into contact with an ingestible liquid, preferably food, characterized in that it comprises at least one support (cap) and / or at least one container for the technological aid. Brief description of the drawings Fig.l

[0015] [Fig.l] [Fig.l] is a photograph of a pellet according to the invention. Fig. 2

[0016] [Fig.2] [Fig.2] is a photo of the neck of a wine bottle closed with a cap being a device for bringing the technological aid into contact with said cap outside the bottle and a cross-section of said cap. Fig. 3

[0017] [Fig.3] [Fig.3] is a photo of a device, in the form of a drop for the implementation contact of the technological aid in the form of a cage. Fig. 4

[0018] [Fig.4] [Fig.4] is a graphical representation of the concentrations in different metals in wine samples. Fig. 5

[0019] [Fig.5] [Fig.5] is a graphical representation of the Fe content of a pellet after treatment according to the invention. Fig. 6

[0020] [Fig.6] [Fig.6] is a graphical representation of the Mn content of a pellet after treatment according to the invention. Fig. 7

[0021] [Fig.7] [Fig.7] is a graphical representation of the Cu content of a pellet after treatment according to the invention. Fig. 8

[0022] [Fig.8] [Fig.8] is a graphical representation of the Zn content of a pellet after treatment according to the invention. Fig. 9

[0023] [Fig.9] [Fig.9] is a graphical representation of the Pb content of a pellet after treatment according to the invention. Fig. 10

[0024] [Fig. 10] [Fig. 10] is a graphical representation of the evolution of Pb concentration in wine samples. Fig. 11

[0025] [Fig. 11] [Fig. 11] is a graphical representation of the evolution of Cu concentration in wine samples. Fig. 12

[0026] [Fig. 12] [Fig. 12] is a graphical representation of the evolution of the concentration of different metals in wine samples. Fig. 13

[0027] [Fig. 13] [Fig. 13] is a graphical representation of the evolution of the concentration of different metals in wine samples. Fig. 14

[0028] [Fig. 14] [Fig. 14] is a graphical representation of the evolution of the concentration of different metals in wine samples. Fig. 15

[0029] [Fig. 15] [Fig. 15] is a graphical representation of the concentration of different metals in wine samples. Definition

[0030] In the present disclosure, all %, ppm and ppb are indicated by mass, unless otherwise stated.

[0031] For the purposes of the present disclosure, "chitosan" means a natural polymer of the co-polysaccharide type, consisting of a random distribution (statistical co-polysaccharide) or not (block or sequence co-polysaccharides) of D-glucosamine (GlcN) and N-acetyl-D-glucosamine (GlcNAc), or even exclusively of D-glucosamine, linked by glycosidic bonds of the [3(1 ->4] type. Chitosan is not very present in the native state in biomass, it is mainly obtained by chemical modification of chitin, of which it is a derivative. Chitin has a structural role, it is found mainly in certain fungi of which it constitutes the cell wall (Basidiomycetes e.g.: Agariscus campestris, Agariscus bisporus, Ascomycetes, Zygomycetes, and Deuteromycetes), but it also forms the exoskeleton of arthropods (crustaceans, insects) notably in shrimp or crab and the endoskeleton of cephalopods such as squid or cuttlefish.The transition from chitin to chitosan is achieved by deacetylation, i.e. by alkaline hydrolysis of the acetyl groups to generate primary amine groups. Chitosan is a biodegradable and biocompatible polymer, with bacteriostatic and fungistatic properties.

[0032] By "gel" is meant a non-fluid polymer network that is swollen by a solvent. The polymer network is a network consisting of crosslinked polymer chains. The interactions responsible for crosslinking polymers can be physical or chemical.

[0033] By "hydrogel" is meant a viscoelastic material comprising at least 60% by mass of water, and preferably at least 80% by mass of water.

[0034] In the context of the invention, the hydrogel is said to be physical, because the interactions responsible for the inter-chain crosslinking giving the hydrogel its cohesion are of the physical type, and are in particular hydrogen bonds and / or hydrophobic interactions, as opposed to a so-called chemical hydrogel (also called crosslinked hydrogel), in which the inter-chain interactions are of the covalent bond type. No chemical crosslinking agent is present in a purely physical hydrogel.

[0035] By "xerogel" is meant a material obtained by drying, in particular drying of a hydrogel, comprising less than 60% by mass of water, preferably less than 50% by mass of water and more preferably less than 20% by mass of water.

[0036] By "aerogel" is meant a material structurally similar to a hydrogel but in which the water has been replaced by gas by a process avoiding the impact of the capillary forces of the solvent on the material (cf. Mike Robitzer, Laurent David, Cyrille Rochas, Francesco Di Renzo and Françoise Quignard Nanostructure of calcium alginate aerogels obtained from multistep solvent exchange route, Langmuir 2008, 24, 12547-12552, and Mike Robitzer, Laurent David, Cyrille Rochas, Francesco Di Renzo and Françoise Quignard, Supercritically-dried alginate aerogels retain the fibrillar structure of the hydrogels, Macromol. Symp. 2008, 273, 80-84).

[0037] In the context of the invention, the average molar masses by mass (Mw) are determined by size exclusion chromatography, the experimental conditions of which are described in the publication “Physico-chemical studies of the gelation of chitosan in a hydroalcoholic medium” A. MONTEMBAULT, C. VITON, A. DOMARD, Biomaterials, 26(8), 933-943, 2005.

[0038] The degree of acetylation (DA) is determined using the proton NMR technique, following the methodology of Hirai (A. HIRAI, H ODANI, A. NAKAJIMA, Polymer Bulletin, 26 (1), 87-94, 1991). Detailed description

[0039] As mentioned above, the invention relates to a method for treating an ingestible liquid, preferably food, consisting essentially of bringing said ingestible liquid into contact with a gel, said gel comprising at least one random polysaccharide of formula I having a weight-average molecular mass Formula I in which Rc is a group comprising a chelating agent, Z is a binder which may be a single bond or a hydrocarbon chain comprising between 1 and 12 carbon atoms, said chain being able to be linear or branched, being able to comprise one or more unsaturations and being able to comprise one or more heteroatoms, preferably chosen from nitrogen, oxygen, sulfur and atoms of the halogen family, x is between 0.005 and 0.6, y is between 0.05 and 0.5, the ratio y / x being greater than 0.2, and the sum x + y being greater than 0.1. The treatment

[0040] The treatment according to the invention makes it possible to reduce the content of metallic elements which are harmful from a health point of view and / or from a conservation point of view without negatively alter the initial taste profile.

[0041] In particular, the treatment comprises an extraction of at least one metal. The extraction of at least one metal not only reduces the risks of oxidation which deteriorates the wine during its conservation, but also reduces the risks of microbial development.

[0042] In one embodiment, said metal is present at a concentration of less than 1 mg / L in the ingestible liquid before implementing the treatment method according to the invention.

[0043] In other words and in particular, in the method according to the invention the treatment comprises an extraction of at least one metal preferably present at a concentration of less than 1 mg / L, or even 0.1 mg / L in the ingestible liquid before the implementation of the method. The ingestible liquid

[0044] The ingestible liquid, preferably food, can be of any nature. The method according to the invention is however particularly suitable for a beverage having an alcohol content greater than or equal to 3% by volume and - in increasing order of preference - 3.5; 4; 4.5; 5 and / or having a pH less than or equal to - in increasing order of preference - 6; 5; 4.

[0045] In one embodiment, the food liquid is a wine, a beer or a spirit. The frost

[0046] The gel used in the treatment method according to the invention has no impact on the main mineral elements present in the ingestible liquid, in particular wine, on the other hand it makes it possible to extract a large proportion of the transition metals involved in the oxidation reactions such as iron, manganese and copper, these being generally present at a concentration around 0.1 mg / L to 1 mg / L. The gel used in the treatment method according to the invention also makes it possible to reduce the content of heavy metals, even those present in trace amounts of the order of approximately 1 pg / L.

[0047] One of the advantages of the gel used in the treatment method according to the invention is that it can be brought directly into contact with the ingestible liquid.

[0048] Another advantage of the gel used in the treatment method according to the invention is that it can be extracted from the ingestible liquid, before ingestion of said ingestible liquid.

[0049] An additional advantage of the gel used in the treatment method according to the invention is its strong hydrophilic character which makes it possible to drastically limit the risks of capturing aromatic organic molecules. In addition, this strong hydrophilic character gives a swelling character to the gel which promotes the availability chelating sites within the ingestible liquid.

[0050] In a particular embodiment of the invention, the gel is a hydrogel or a xerogel, preferably in compact form (e.g. pellet, beads, blocks) or particulate form (e.g. powder).

[0051] According to the invention, the gel comprises at least one statistical polysaccharide of formula I having a weight-average molecular mass of between 100 kDa and 1000 kDa: Formula I

[0052] Advantageously, 1 kg of gel contains between 40 g and 100 g of random polysaccharide of formula I, more advantageously between 45 g and 75 g, even more advantageously approximately 50 g.

[0053] Advantageously, x is between 0.05 and 0.6, preferably between 0.1 and 0.35.

[0054] Advantageously, y is between 0.05 and 0.4, preferably between 0.1 and 0.3

[0055] It is understood that, in formula I above, several Rc groups may be present in the polysaccharide. These Rc groups may be identical or different from each other. All the Rc groups are independently chosen from the groups carrying a chelating agent. The same applies to the Z binders: several Z binders may be present, and they may be identical or different from each other.

[0056] In particular, the random polysaccharide included in the gel may be of formula II: Formula II in which: - Rci and Rc2 are different, and are groups containing a chelating agent, - Zi and Z2, identical or different, are binders which can be a simple bond or a hydrocarbon chain comprising between 1 and 12 carbon atoms, said chain being able to be linear or branched and being able to comprise one or more unsaturations and being able to comprise one or more heteroatoms, preferably chosen from nitrogen, oxygen, sulfur and atoms of the halogen family, - x is between 0.005 and 0.6, preferably between 0.01 and 0.3, and preferably between 0.05 and 0.1, - y is between 0.05 and 0.5, preferably between 0.05 and 0.2, - z is between 0 and 0.2.

[0057] In the present disclosure, the term Rc type group means the Rc groups in the polysaccharide of formula I, and the Rci and Rc2 groups, when the Rc2 group is present, in the polysaccharide of formula II.

[0058] According to the invention, the Rc, Rci and Rc2 groups are chelating agents. In other words, the Rc, Rci and Rc2 groups make it possible to chelate one or more metals by forming a complex.

[0059] Each of the groups Rc, Rci and Rc2 may contain one or more coordination sites. Preferably, the coordination site is a nitrogen or oxygen atom. Advantageously, each of the groups Rc, Rci and Rc2 comprises between 4 and 8 coordination sites, more advantageously between 6 and 8 coordination sites and even more advantageously each of the groups Rc, Rci and Rc2 comprises 8 coordination sites.

[0060] A coordination site is understood to mean a single function capable of binding to a metal. For example, an amine function represents a coordination site by the formation of a dative bond between the nitrogen atom and the metal and a hydroxamic acid function also represents a coordination site by the formation of a dative bond between the oxygen of the carbonyl unit and by a covalent bond with the oxygen of the N-oxide unit, the coordination site thus forming a five-atom cycle.

[0061] In one embodiment of the invention, for the polysaccharide of formula I, each Rc group is independently selected from the group consisting of DOTA (1,4,7,10-tetraazacyclododecane-N,N',N”,N”'-tetraacetic acid), NOTA (1,4,7-triazacyclononane-1,4,7-triacetic acid), NODAGA (1,4,7-triazacyclononane-1-glutaric acid-4,7-diacetic acid), DOTAGA (2-(4,7,10-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecan-1-yl)pentanedioic acid), DOTAM (1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane), NOTAM ( 1,4,7-tetrakis(carbamoylmethyl)-1,4,7-triazacyclononane), DOTP (1,4,7,10-tetraazacyclododecane 1,4,7,10-tetrakis(methylene phosphonate), NOTP (l,4,7-tetrakis(methylene phosphonate)-l,4,7-triazacyclononane), TETA (1,4,8,1 l-tetraazacyclotetradecane-N,N' ,N' ',N' ”-teraacetic acid), TETAM (1,4,8,11 -tetraazacyclotetradecane-N,N' ,N” ,N” '-tetrakis(carbamoyl methyl), DTPA (diethylene triaminopentaacetic acid), NTA (nitrilotriacetic acid) and DFO (deferoxamine), preferably from the group consisting of DOTAGA, EDTA, DOTAM and DTPA and more preferably the Rc group is DOTAGA.

[0062] In one embodiment of the invention, for the polysaccharide of formula II, Rci and Rc2 are independently selected from the group consisting of DOTA, NOTA, NODAGA, DOTAGA, DOTAM, NOTAM, DOTP, NOTP, TETA, TETAM, DTPA and DFO, preferably from the group consisting of DOTAGA, DFO, DOTAM and DTPA.

[0063] According to one embodiment, for the polysaccharide of formula II, the Rci group is DOTAGA, and preferably, z=0.

[0064] According to one embodiment, for the polysaccharide of formula II, the Rci group is DOTAGA and the Rc2 group is DFO.

[0065] In the present disclosure, the term "Z-type binder" means the Z-linkers in the polysaccharide of formula I, and the Zi and Z2 binders, when the Z2 binder is present, in the polysaccharide of formula II.

[0066] The choice of spacers Z, Zi and Z2 in formulas I and II depends essentially on the groups Rc, Rci and Rc2 and the metal to be chelated. Indeed, for steric reasons in particular, the groups Rc, Rci and Rc2 can be more or less close to the nitrogen of the glucosamine unit.

[0067] Preferably, in formula I, each Z is independently a single bond or a hydrocarbon chain comprising between 1 and 12 carbon atoms, said chain possibly being linear or branched and possibly comprising one or more unsaturations and possibly comprising one or more heteroatoms, preferably chosen from nitrogen, oxygen, sulfur and atoms of the halogen family.

[0068] According to one embodiment, in formula I, each Z is independently selected from the group consisting of a bond, a linear or branched alkyl chain having between 1 and 12 carbon atoms, and a linear or branched alkenyl chain having between 2 and 12 carbon atoms, said alkyl and alkenyl chains possibly being interrupted by one or more C6-C10 aryl groups, and / or by one or more heteroatoms or groups selected from the group consisting of -O-, -S-, -C(O)-, -NR'-, -C(O)NR'-, -NR'-C(O)-, -NR'-C(O)-NR'-, -NR'-C(O)-O-, -OC(O)NR', ​​-C(S)NR'-, -NR'-C(S)-, -NR'-C(S)-NR' said alkyl and alkenyl chains may be substituted by one or more groups selected from the group consisting of halogens, -OR', -COOR', -SR', -NR'2j each R' is independently H or C1-C6 alkyl.

[0069] Advantageously, in formula I, each Z is independently selected from the group consisting of: a bond and a linear or branched alkyl chain comprising between 1 and 12 carbon atoms, said alkyl chain may be interrupted by one or more C6-C10 aryl groups, and / or by one or more heteroatoms or groups selected from the group consisting of -O-, -S-, -C(O)-, -NR'-, -C(O)NR'-, -NR'-C(O)-, -C(S)NR'-, -NR'-C(S)-, -NR'-C(S)-NR', each R' is independently H or C1-C6 alkyl

[0070] In a particular embodiment, each Z is an alkyl chain comprising between 1 and 12 carbon atoms.

[0071] In another particular embodiment, each Z is a polyethylene glycol (PEG) segment.

[0072] Preferably, in formula II, Zi and Z2 are independently a single bond or a hydrocarbon chain comprising between 1 and 12 carbon atoms, said chain possibly being linear or branched and possibly comprising one or more unsaturations and possibly comprising one or more heteroatoms, preferably chosen from nitrogen, oxygen, sulfur and atoms of the halogen family.

[0073] According to one embodiment, in formula II, Zi and Z2 are independently selected from the group consisting of: a bond, a linear or branched alkyl chain comprising between 1 and 12 carbon atoms, and a linear or branched alkenyl chain comprising between 2 and 12 carbon atoms, said alkyl and alkenyl chains being able to be interrupted by one or more C6-Ci0 aryl groups, and / or by one or more heteroatoms or groups selected from the group consisting of -O-, -S-, -C(O)-, -NR'-, -C(O)NR'-, -NR'-C(O)-, -NR'-C(O)-NR'-, -NR'-C(O)-O-, -OC(O)NR', ​​-C(S)NR'-, -NR'-C(S)-, -NR'-C(S)-NR' said alkyl and alkenyl chains may be substituted by one or more groups selected from the group consisting of halogens, -OR', -COOR', -SR', -NR'2j each R' is independently H or C1-C6 alkyl.

[0074] Advantageously, in formula II, Zi and Z2 are independently selected from the group consisting of: a bond and a linear or branched alkyl chain comprising between 1 and 12 carbon atoms, said alkyl chain may be interrupted by one or more C6-C10 aryl groups, and / or by one or more heteroatoms or groups selected from the group consisting of -O-, -S-, -C(O)-, -NR'-, -C(O)NR'-, -NR'-C(O)-, -C(S)NR'-, -NR'-C(S)-, -NR'-C(S)-NR', each R' is independently H or C1-C6 alkyl.

[0075] In a particular embodiment, Zi and / or Z2 is an alkyl chain comprising between 1 and 12 carbon atoms.

[0076] In another particular embodiment, Zi and / or Z2 is a polyethylene glycol (PEG).

[0077] According to the invention, z is between 0 and 0.2. In other words, the C-type units can be exclusively units comprising Zi as a binder and Rci as a group carrying a chelating agent.

[0078] The statistical polysaccharide of formula I has a weight average molecular mass of between 100 kDa and 10000 kDa, advantageously, the weight average molecular mass of the polysaccharide according to the invention is between 200 kDa and 7500 kDa, more advantageously between 250 kDa and 5000 kDa and even more advantageously, between 300 kDa and 4000 kDa.

[0079] In a particular embodiment, said gel further comprises a chitosan.

[0080] Advantageously, the chitosan has an average molecular mass Mw of between 100 kg / mol and 1000 kg / mol, preferably between 200 kg / mol and 700 kg / mol.

[0081] According to a preferred embodiment, the chitosan has a degree of acetylation of less than 40%, preferably less than 10%, for example between 0% and 10%.

[0082] When the gel comprises a chitosan, said chitosan advantageously represents between 30% and 70% by weight of said gel. Contacting

[0083] The method for treating an ingestible liquid according to the invention essentially consists of bringing said ingestible liquid into contact with the gel described above. The contacting can be done by any means. For example, the contacting can be done by simple deposit of the gel in the liquid, with or without stirring, or by means of a support containing said gel and through which said liquid can pass.

[0084] Depending on the liquid to be treated and the contacting method, several parameters need to be adapted. For example, in the context of contacting by simple deposition without stirring, the contacting time will necessarily be longer than in the context of contacting by simple deposition but with stirring, to obtain the same extraction rate of a metal. Another parameter is the gel dosage and therefore the number of Rc groups available for metal chelation.

[0085] Generally, the contact between the gel and the ingestible liquid is at least one hour, and can last more than 24 hours. Other aspects of the invention

[0086] As mentioned above, the invention also relates to a method for manufacturing an ingestible liquid, preferably food, characterized in that it integrates in one or more of its steps, the treatment specific to the method for treating an ingestible liquid mentioned above.

[0087] The treatment method can be implemented in any step of the manufacturing cycle of an ingestible liquid. In one embodiment, the treatment method according to the invention is advantageously implemented as the last step in the manufacturing of a food liquid.

[0088] As indicated previously, the invention is also directed towards a technological aid for implementing the method of treating an ingestible liquid characterized in that it comprises at least one body in compact form (e.g. pellets, beads, blocks) or particulate form (e.g. powder) of a gel as defined above. [Fig.l] is a photo of a pellet according to the invention.

[0089] According to an alternative, the invention further relates to a composition for treating an ingestible liquid, preferably food, characterized in that it contains the technological auxiliary described above and at least one other agent for treating or adjuvanting the ingestible liquid.

[0090] In particular, the invention is characterized by a device for bringing the technological aid described above into contact with an ingestible liquid, preferably food-grade, characterized in that it comprises at least one support and / or at least one container for the technological aid.

[0091] This device may comprise a cap supporting the technological aid, a capsule containing the technological aid or a perforated container.

[0092] To allow the ingestible liquid to come into contact with the technological aid, the device advantageously has an opening. Thus, the technological aid can be inserted into a compartment having at least one opening. The support can be a wine bottle stopper as illustrated in [Fig.2], a wine bottle or beer bottle cap, or a cage for holding the technological aid in a defined space through which the ingestible liquid can pass. Such a cage can have the shape of a drop of liquid as illustrated in [Fig.3].

[0093] The method according to the invention being particularly effective, it is possible to obtain ingestible liquids comprising less than 50 pg / L of copper, preferably less than 20 pg / L of copper, and / or less than 10 pg / L of lead, preferably less than 5 pg / L of lead.

[0094] Thus, and in particular, the invention also relates to an alcoholic beverage comprising less than 50 pg / L of copper, preferably less than 20 pg / L of copper, and / or less than 10 pg / L of lead, preferably less than 5 pg / L of lead. Examples

[0095] Synthesis and characterization of polymers for the manufacture of pellets Synthesis of compound 1 (MEX-CD2)

[0096] The chitosan precursor of the MEX-CD2 polysaccharide is of medical grade and animal origin. The weight and number average molar masses (respectively Mw = 2,583.105 g / mol, Mn = 1,323.105 g / mol) were determined by size exclusion chromatography coupled with refractive index and multi-angle laser light scattering measurements. The degree of acetylation (proportion of N-acetyl-D-glucosamine unit) of such crude chitosan was determined by 'H NMR spectroscopy using the Hirai method (Asako Hirai et al., Determination ofdegree of deace-tylation of chitosan by 'H NMR spectroscopy, Polymer Bulletin, 1991, 26, 87-94) and is estimated to be 6.0 ± 0.5%. 60 g of chitosan are introduced into a 10 L reactor with 4 L of ultrapure water and 50 mL of acetic acid, and then the mixture is placed under mechanical stirring at 500 RPM.After complete dissolution of the chitosan (3h), 4L of 1,2-propanediol are added to the medium and the mixture is kept stirring until homogenized (2h). 120g of DOTAGA anhydride are then introduced and the mixture is kept stirring overnight until complete dissolution. The synthesis product is then purified by tangential filtration using the Sartoflow® Advanced device with a Sartocon® Slice PESU cassette (polyethersulfone membranes; cut-off threshold: 100 kDa; filtration area: 0.1 m2) according to a diafiltration-concentration model against 200L of a 0.1M acetic acid solution then 200L of a 5mM acetic acid solution. Purification is followed by size exclusion chromatography coupled with a UV detector until less than 5% of free DOTAGA is obtained.The product is then lyophilized and the degree of acetylation (DA) and the degree of substitution (DS) are determined respectively by 'H NMR and by the copper chelation method described below. The obtained polymer has a DOTAGA grafting rate of 15%. The purity was verified by HPLC as mentioned below. Synthesis of compound 2 (MEX-DTPA)

[0097] The chitosan precursor of the polysaccharide MEX-DTPA (compound 2) is of medical grade and of animal origin. The weight and number average molar masses (respectively Mw = 1.590.105 g / mol, Mn = 1.23 8.105 g / mol) were determined by size exclusion chromatography coupled with refractive index and multi-angle laser light scattering measurements. The degree of acetylation (proportion of N-acetyl-D-glucosamine unit) of such crude chitosan was determined by 'H NMR spectroscopy by the Hirai method (Asako Hirai et al., Determination ofdegree of deace-tylation of chitosan by 'H NMR spectroscopy, Polymer Bulletin, 1991, 26, 87-94) and is estimated at 6.6 ± 0.5%.

[0098] 10 g of chitosan are dissolved in 660 mL of ultrapure water with 8.39 mL of acid glacial acetic acid, then the mixture is stirred at room temperature until completely homogenized. 100 mL of this solution is then placed in a flask, to which 100 mL of ultrapure water is added to obtain a chitosan concentration of 7.5 g / L. 428 mg of DTPA-bis anhydride is then added to the solution, then heated to 30°C to allow the DTPA to dissolve. The medium is stirred overnight. The synthesis product is then purified several times by tangential filtration using the Sartoflow® Advanced device with a Sartocon® Slice PESU cassette (polyethersulfone membranes; cut-off threshold: 100 kDa; filtration area: 0.1 m2) according to a diafiltration-concentration model against 20 L of a 10 mM hydrochloric acid solution. The product is then lyophilized and the degree of acetylation (DA) and degree of substitution (DS) are determined respectively by 'H NMR and by the copper chelation method described below.The obtained polymer has a DTPA grafting rate of 5.8%. The purity was verified by HPLC as mentioned below. Characterization of polymers

[0099] The degree of acetylation (DA) of compounds 1 and 2 is obtained as follows: The 'H NMR spectra of the products to be analyzed are obtained using a Bruker Avance III HD 400 MHz NanoBay spectrometer. The phase is manually corrected using the water peak located at 4.7 ppm. The peaks are integrated manually by integrating the peak mass between 4.1 and 2.9 ppm and by integrating the peak at 2.00 ppm between 2.02 and 1.90 ppm. The percentage DA is directly obtained by normalizing the integration of the peak mass to 200.

[0100] The degree of substitution (DS) in chelate (DOTAGA for compound 1; DTPA for compound 2) is obtained as follows: Different samples of the product to be analyzed are obtained by dispersing the lyophilized product in an acetate buffer (0.1 M acetic acid and 0.1 M ammonium acetate) to obtain a final polymer mass concentration of 0.1%. Different volumes of a copper nitrate solution are added to obtain copper concentrations in each sample ranging from 0 to 1 mM and then each sample is stirred. The absorbance of the resulting solutions is then measured using a Varian Cary® 50 UV-Visible spectrophotometer. The determination of the DS is carried out by plotting the absorbance at 295 nm as a function of the copper concentration, the break corresponding to the amount of chelate per 1 g of product.

[0101] The purity of compounds 1 and 2 is verified as follows: The HPLC-SEC-UV chromatograms of the products to be analyzed were recorded on samples at a polymer mass concentration of 1% with an HPLC system Shimadzu Prominence. The SEC column used is a Shodex OHpak SB-805 HQ column for compound 2 and PolySep-GFC-P 4000 for compound 1 and an acetate buffer is used as eluent (0.1 M acetic acid and 0.1 M ammonium acetate). The operating temperature is 30°C and the absorption wavelength is 295 nm. The eluent flow rate is 0.8 mL / min. The purity of the product is verified by integration of the free DOTAGA peak on the integration of the DOTAGA-grafted chitosan peak.

[0102] Example 1 - MEX-CD2 (compound 1) pellet(s) immersed in a small volume of wine

[0103] Pellets of compound 1 are prepared as follows: 16.76 mL of ultrapure water, 240 μL of glacial acetic acid, 2.01 g of compound 1 (MEX-CD2) and 990 mg of chitosan are introduced into a 100 mL reactor with mechanical stirring at 100 RPM. The mixture is left stirring for 1 h until complete dissolution and homogenization of the medium. The solution obtained is transferred into a 50 mL dispenser and then centrifuged for 5 minutes at 3500 RPM to remove air bubbles. The solution is placed in PVC molds with dimensions 0=1 cm and h=2 mm. After the solution has spread uniformly, the mold containing the solution is introduced into a 3M sodium hydroxide (NaOH) bath for 30 minutes. This is then transferred to a bath of ultrapure water to rinse the soda for 1 hour, then the pellets obtained are removed from the molds and placed in a second bath of 4.5 L of ultrapure water.The pH is measured every thirty minutes to check that the pellets are properly rinsed. After 2 hours, the bath is replaced with 4L of ultrapure water and left stirring for 2 days. The pellets are then dried at room temperature for 24 hours.

[0104] Ten wines from a Côtes du Rhône estate, of different types and different vintages were used, all coming from the Domaine de la Catherinette located in Laval Saint Roman: - 2 red Côtes du Rhône (2020 and 2021), - 2 Côtes du Rhône rosé (2020 and 2021), - 2 white Côtes du Rhône (2020 and 2021), - 2 Viogniers (2020 and 2021), - 1 Syrah (2020), and - 1 Marselan (2020).

[0105] For each of the wines, 5 bottles containing 15 ml of said wine are prepared. Bottle No. 1 is used as a control without the addition of a tablet, one tablet is added to each bottle 2, 3 and 4, two tablets are added to bottle No. 5. Samples of 0.2 ml of wine are taken after 215 hours and analyzed by ICP-MS according to the following protocol:

[0106] ICP-MS analyses of metals are performed using an Agilent 7850 series ICP-MS mass spectrometer equipped with a quadrupole analyzer and an integrated sample changer.

[0107] The operating conditions of the device are as follows: [Tab. 1] Plasma power 1550 W Sampling depth (cone-torch distance) 8 mm Plasma gas flow rate (Ar) 15 L / min Carrier gas flow rate (Ar) 1 L / min Additional gas flow rate (Ar) 1 L / min Collision gas flow rate (He) 4.3 mL / min

[0108] The conditions for semi-quantitative acquisitions are as follows: [Tab. 2] Acquisition mode Spectrum Standard Standard 28 elements at 20 ppb Blank HN03 1% Number of masses 60 Integration time 0.6 sec / point Number of points per mass 6 Acquisition time 216 sec Number of repetitions 1 Sample collection time 50 sec Stabilization time 30 sec Post-acquisition rinse 3 x 45 sec Total analysis time 431 sec

[0109] Just before analysis, the wine and pellet samples are diluted by 15 in 1% HN03.

[0110] The quantities of Iron (Fe), Manganese (Mn), Copper (Cu) and Zinc (Zn) in bottles No. 1, No. 2, No. 3 and No. 4 of the 2020 wines were measured. The results are shown in [Fig. 4]. All concentrations of Fe, Mn, Cu and Zn are significantly reduced in the six wines treated with a tablet according to the invention.

[0111] The pellets present in bottles No. 2, No. 3 and No. 4 of each of the wines were analyzed to determine their respective content of Fe ([Fig. 5]), Mn ([Fig. 6]), Cu ([Fig. 7]), Zn ([Fig. 8]) and lead (Pb) ([Fig. 9]). Figures 5 to 9 show that Fe, Mn, Cu, Zn and Pb are captured by the pellet according to the invention and remain encapsulated in the pellet.

[0112] The Pb concentrations in bottles No. 1 to No. 5 of all the wines were measured ([Fig. 10]).

[0113] A significant reduction in the quantity of lead is observed, even for initial concentrations of around ten ppb. These results show that it is possible to reduce the quantity of lead below 5 ppb and even below 1 ppb in wine after adding pellets.

[0114] This result is very promising with a view to using these tablets to decontaminate wine from these heavy metals, lead in particular being known to have an impact on cardiovascular diseases.

[0115] The Cu concentrations in bottles No. 1 to No. 5 of all the wines were measured ([Fig. 11]).

[0116] It is observed that when the Cu concentration is initially high, the addition of a second pellet (bottles no. 5) makes it possible to further reduce the Cu concentration at the end of the treatment.

[0117]

[0118] Example 2 - MEX-DTPA (compound 2) pellet(s) immersed in wine

[0119] Pellets of compound 2 are prepared as follows: 6 mL of water ultrapure, 305 μL of glacial acetic acid, 353 mg of compound 2 (MEX-DTPA) and 706 mg of chitosan are added under mechanical stirring at 100 RPM in a 100 mL reactor. The mixture is left stirring for 1 h until complete dissolution and homogenization of the medium. The solution obtained is transferred into a 50 mL dispenser and then centrifuged for 5 minutes at 3500 RPM to remove air bubbles. The solution is placed in PVC molds with dimensions 0=1 cm and h=2 mm. After the solution has spread evenly, the mold containing the solution is introduced into a 3M sodium hydroxide (NaOH) bath for 30 minutes. This is then transferred to a bath of ultrapure water to rinse the soda for 1 hour, then the pellets are removed from the molds and placed in a second bath of 4.5 L of ultrapure water. The pH is measured every thirty minutes to check the rinsing of the pellets.After 2 hours, the bath is replaced with 4L of ultrapure water and the whole mixture is left stirring for 2 days. The pellets are then dried at room temperature for 24 hours and then weighed: an average mass of 25.6 mg per pellet is obtained.

[0120] In order to evaluate the chelation capacities of the lozenges, 4 glass bottles are filled of 100 mL according to the following arrangement: In the four bottles, 100 mL of red wine (Château Merigot 2018, Côtes de Bourg, Dominique Raimond) is introduced. Bottle No. 1 is used as a control without adding a tablet, one tablet is added to bottle 2, two tablets are added to bottle 3 and three tablets are added to bottle 4. The following table summarizes the different masses of the tablets added: [Tab. 3] Sample n VR0P VR1P VR2P VR3P n°pellet - 1 2 3 4 5 6 mpellet (mg) - 26.4 26.6 25.5 26.4 24.2 27.8 mtot (mg) - 26.4 52.1 78.4

[0121] 1 mL samples from each vial are taken at different time points (t = 0 h, 164 h, 267 h, 667 h, 141 h, 1680 h); the samples are stored in 2 mL metal-free VWR tubes.

[0122] After the last sample, the pellets are removed from the medium, weighed and then dissolved in 3 mL of 69% (w / w) nitric acid and 1 mL of ultrapure water for one hour. The following table summarizes the masses of the pellets collected after 70 days in the wine and listed in the following table: [Tab. 4] Sample VR0 P VR1 P VR2 P VR3 P Number of pellets 0 1 2 3 Total mass of pellets (mg) 0 55 112 183

[0123] The redispersed pellets, as well as the wine samples, are analyzed by semi-quantitative ICP-MS according to the above method after dilution by 15 in 1% (w / w) nitric acid.

[0124] Elemental analysis of wine samples shows a decrease in the concentration of several metals over time.

[0125] It can be seen in Figures 12, 13 and 14 that the decrease in the concentration of Fe, Zn, Mn and Ni increases as the number of pellets increases. Furthermore, regardless of the number of pellets added, the concentrations in the wine of Fe, Zn, Mn and Ni decrease overall over time after the addition of the pellets.

[0126] The pellets recovered from the flasks and then redispersed were also analyzed by elemental analysis. The following table summarizes the masses of Fe, Zn, Mn and Ni in the pellets after dissolution in 52% nitric acid (3 mL HN03 69% + 1 mL H2O), as well as the masses obtained per pellet: [Tab. 5] Fe Mn Cu Zn VR1P Total mass captured (pg) 291 44.2 15.1 148 Mass captured per pellet (pg) 291 44.2 15.1 148 VR2P Total mass captured (Pg) 612 83.1 25.1 286 Mass captured per pellet (pg) 306 41.55 12.55 143 VR3P Total mass captured (Pg) 782 133 35.2 367 Mass captured per pellet (pg) 261.5 44.33 11.73 123.33

[0127] the mass captured per pellet varies little regardless of the number of pellets for a given metal, thus, the total quantity of metal captured in the wine is proportional to the number of pellets introduced.

[0128] Example 3 - MEX-CD2 pellet (compound 1) immersed in the wine bottle

[0129] Pellets of compound 1 are prepared as follows: 20.95 mL of ultrapure water, 286 μL of glacial acetic acid, 2.513 g of the obtained polymer (MEX-CD2) and 1.238 g of chitosan are added under mechanical stirring at 100 RPM in a 100 mL reactor. The mixture is left stirring for 1 h until complete dissolution and homogenization of the medium. The solution obtained is transferred into a 50 mL dispenser and then centrifuged for 10 minutes at 4000 RPM to remove air bubbles. The solution is placed in PVC molds with dimensions 0=1.5 cm and h=8 mm. After the solution has spread uniformly, the mold containing the solution is introduced into a 3M sodium hydroxide (NaOH) bath for 1 h. This is then transferred to a bath of ultrapure water to rinse the soda for 2 hours, then the pellets are removed from the molds and placed in a second bath of 10 L of ultrapure water overnight. The pH is then measured (pH = 10.42), then the bath is replaced with 10 L of ultrapure water and changed after 4 hours (pH = 10.12). The whole is then left stirring for 48 hours. The pellets are then transferred into a 200 mL bath of ultrapure water, then the pH is measured after 2 hours (pH = 7.94). The pellets are weighed: an average mass of 3.53 g per pellet is obtained. The pellets are then dried at 37°C for 24 hours and then weighed; the following table summarizes the masses of the pellets obtained:

[0130] [Tab. 6] tablet number 1 2 3 4 5 6 7 8 9 Mass (mg) 167 171 164 162 125 162 130 196 145

[0131] In order to evaluate the chelation capacities of the pellets, the following protocol is implemented: 12 bottles of wine are used: 6 bottles of white wine (Petit Chablis 2020, Domaine Yvon & Laurent Vocoret) and 6 bottles of red wine (Château Merigot 2018, Côtes de Bourg, Dominique Raimond). For the twelve bottles are opened then a pastille is introduced into four bottles of Petit Chablis and into four bottles of Château Merigot, in two bottles of each wine no pastille is added. The twelve bottles are then closed.

[0132] After 3.5 months, 3 bottles of each wine are opened (2 with tablets and one without a tablet), a sample of the wine (20 mL) is taken and the tablets are collected and weighed then dissolved in 3 mL of 69% (w / w) nitric acid and 1 mL of ultrapure water for one hour. The redispersed tablets, as well as the wine samples, are analyzed by semi-quantitative ICP-MS after dilution by 15 in 1% (w / w) nitric acid. The following table summarizes the masses of the tablets collected after 3.5 months in the wine: [Tab. 7] Sample mass (mg) Average mass (mg) CHABLIS 1 327.6 376.45 CHABLIS 2 425.3 MERIGOT 1,302.8 348.05 MERIGOT 2,393.3

[0133] [Fig. 15] shows the concentrations of different metals in the samples as a percentage compared to the concentration in the bottles without tablets. For Fe, Mn and Zn, the concentration in the wines decreases with treatment with a tablet, with decreases on average being more pronounced (>20%) for the white wine. Concerning Cu, Ni and Pb, a strong decrease in the concentration in the white wine is observed, whereas in the red wine these metals are not significantly captured by the tablet.

[0134] The metal concentration in the pellets after redispersion was also evaluated; in order to obtain only the captured metal concentration, the metal concentration in a dry pellet redispersed in 3 mL of 69% (w / w) nitric acid and 1 mL of ultrapure water was subtracted. The following table summarizes the average masses of metals extracted by the pellets in the wine:

[0135] [Tab. 8] Mn Fe Cu Zn Co Ni Cd Pb U Mass of metals extracted by the pellet in 3.5 months (pg) in red wine 561 2200 78.5 1140 1.45 0.0445 0.484 0.952 0.019 9 Mass of metals extracted by the pellet in 3.5 months (pg) in white wine 519 1090 119 1170 4.89 8.00 7.24 7.24 0.220

Claims

1. Claims A method of treating an ingestible liquid, preferably food, consisting essentially of bringing said ingestible liquid into contact with a gel, said gel comprising at least one statistical polysaccharide of formula I having a weight-average molecular mass of between 100 kDa and 1000 kDa:

2.

3.

4. Formula I in which Rc is a group comprising a chelating agent, Z is a binder which may be a single bond or a hydrocarbon chain comprising between 1 and 12 carbon atoms, said chain being able to be linear or branched, being able to comprise one or more unsaturations and being able to comprise one or more heteroatoms, preferably chosen from nitrogen, oxygen, sulfur and atoms of the halogen family, x is between 0.005 and 0.6, y is between 0.05 and 0.5, the ratio y / x being greater than 0.2, the sum x + y being greater than 0.

1. Method according to claim 1, characterized in that said gel further comprises a chitosan. Method according to any one of the preceding claims, characterized in that the treatment comprises an extraction of at least one metal preferably present at a concentration of less than 1 mg / L, or even 0.1 mg / L in the ingestible liquid before implementing the method. Method according to any one of the preceding claims, characterized in that the ingestible liquid, preferably food, is a drink having an alcohol content greater than or equal to 3 in % by volume and - in increasing order of preference - 3.5; 4; 4.5; 5 and / or having a pH less than or equal to - in increasing order of preference - 6; 5; 4.

5.

6.

7.

8. Method according to any one of the preceding claims, characterized in that the food liquid is a wine, a beer or a spirit. Method according to any one of the preceding claims, characterized in that the gel is a hydrogel or a xerogel, preferably in compact form (e.g. pellet, beads, blocks) or particulate form (e.g. powder). Process for manufacturing an ingestible liquid, preferably food, characterized in that it integrates in one or more of its steps, the treatment specific to the process according to any one of the preceding claims. Technological aid for implementing the method according to any one of claims 1 to 6, characterized in that it comprises at least one body in compact (e.g. pellets, beads, blocks) or particulate (e.g. powder) form of a gel, said gel comprising at least one statistical polysaccharide of formula I having a weight-average molecular mass of between 100kDa and 1000kDa:

9. Formula I in which Rc is a group comprising a chelating agent, Z is a binder which may be a single bond or a hydrocarbon chain comprising between 1 and 12 carbon atoms, said chain being able to be linear or branched, being able to comprise one or more unsaturations and being able to comprise one or more heteroatoms, preferably chosen from nitrogen, oxygen, sulfur and atoms of the halogen family, x is between 0.005 and 0.6, y is between 0.05 and 0.5, the ratio y / x being greater than 0.2, the sum x + y being greater than 0.

1. Composition for treating an ingestible liquid, preferably food, characterized in that it contains the technological aid according to claim 8 and at least one other treatment agent or adjuvanting the ingestible liquid, preferably food.

10. Device for bringing the technological aid according to claim 8 into contact with an ingestible liquid, preferably food, characterized in that it comprises at least one support and / or at least one container for the technological aid.

11. Device according to claim 10, characterized in that it comprises a stopper supporting the technological auxiliary, a capsule containing the technological auxiliary or an openwork container.

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