Composition in the form of a supramolecular organization including hydrophilic molecules stabilized by mineral particles in a lipid phase

Abstract

A composition comprising unsaturated lipids such as omega 3 and omega 6, antioxidants and phyllosilicate particles, wherein the phyllosilicate particles are clusters of sheets, wherein said antioxidants comprise water-soluble antioxidants dissolved in water adsorbed in the phyllosilicate sheets and wherein the phyllosilicate sheets are dispersed in the composition by an amphiphilic dispersing agent adsorbed on the surface of the phyllosilicate particles. Figure 13

Description

Title of the invention: Composition in the form of a supra-molecular organization including hydrophilic molecules stabilized by mineral particles in a lipid phase Field of invention

[0001] The present invention relates to compositions comprising unsaturated lipids such as omega 3 and omega 6. It particularly relates to a composition whose resistance to oxidation is reinforced, for direct use or as an ingredient in formulations requiring lipids that are more stable to oxidation during the transformation process or during storage. State of the art

[0002] Lipids constitute the fatty matter of living beings. They are hydrophobic or amphiphilic molecules - hydrophobic molecules possessing a hydrophilic domain - very diverse, which can be saturated or unsaturated, including among others fats, waxes, sterols, fat-soluble vitamins, mono-, di- and triglycerides, or even phospholipids.

[0003] They play a role both as an energy reserve, as the main constituent of the membranes of the cells of living beings, and of communication between cells by lipid signaling mechanisms and thus constitute a very important part of human and animal nutrition.

[0004] Unsaturated lipids are molecules sensitive to oxidation. The main factors are temperature, oxygen and light. Lipid oxidation can be initiated by a reaction between reactive oxygen species and an unsaturated fatty acid. This oxidation mechanism is then followed by a propagation and termination step.

[0005] [Fig.l] schematically illustrates the mechanism of oxidation of an unsaturated fatty acid.

[0006] The first step that activates lipids leads to a lipid radical:

[0007] LH + OH • H2O + L ■

[0008] Lipid free radicals react with oxygen to generate peroxyl radicals:

[0009] L • + O2 LOO •

[0010] In the propagation phase, the peroxyl radicals react with other unsaturated fatty acids to form hydroperoxides and a new reactive lipid radical:

[0011] LOO- + L'H LOOH + L'-

[0012] Then, in the termination phase, the hydroperoxides decompose via a radical pathway or a non-radical pathway. The majority of secondary compounds formed are aldehydes, carbonyls, alcohol and hydrocarbons.

[0013] Among these secondary compounds, we find malondialdehyde (MDA) which is a marker of the oxidation of polyunsaturated lipids containing more than two double bonds. Once the oxidation mechanism is initiated, and following the formation of hydroperoxide, the latter will potentially decompose into MDA and 4-hydroxy-2-nonenal (4-HNE).

[0014] Lipid oxidation can thus be monitored by measuring hydroperoxides.

[0015] It has been demonstrated that the oxidation of lipids, and in particular of unsaturated fatty acids such as omega 3 and omega 6, can cause irreversible damage from a metabolic point of view.

[0016] In food matrices, there are two possibilities for introducing lipids. The first is to place them inside the matrix in order to limit the access of UV radiation and oxygen. The second possibility is to place them on the outside as a coating when the food manufacturing process involves high temperatures, in order to limit the consequences of the high temperatures at which the lipids are used.

[0017] Despite everything, in these two cases, the lipids are exposed to potential oxidation either during the process or during storage. In food formulation processes, high temperatures are often used, particularly in the manufacture of pelleted food by extrusion. Furthermore, storage conditions that improve the stability over time of sensitive nutrients, such as atmospheric conditions modified during packaging (vacuum packaging or in a non-oxidizing atmosphere), are rarely or not at all used, and the products are therefore exposed to oxygen.

[0018] There is therefore a growing need for systems that can protect and delay lipid oxidation, while simplifying the implementation of lipid contributions in foods, whether inside or outside food matrices. Brief description of the invention

[0019] The objective of the invention is to propose a composition comprising a system for protecting and delaying the oxidation of unsaturated lipids whether inside or outside food matrices.

[0020] The subject of the invention is a composition comprising unsaturated lipids such as omega 3 and omega 6, antioxidants and phyllosilicate particles, in which the phyllosilicate particles are clusters of sheets, in which the antioxidants comprise water-soluble antioxidants dissolved in the adsorbed water in the phyllosilicate sheets with an antioxidant content greater than 0.01% by weight relative to the weight of the lipids in the composition, and in which the phyllosilicate sheets are dispersed in the composition by an amphiphilic dispersing agent adsorbed on the surface of the phyllosilicate particles.

[0021] The water-soluble antioxidants of the composition dissolved in the swelling and exfoliation water of the phyllosilicates are dispersed and stabilized in the lipid phase by the phyllosilicate particles. The amphiphilic dispersing or surfactant makes it possible to make the external surface of the clusters of sheets partially hydrophobic and thus allows the dispersion and stabilization of these clusters of sheets in the lipid phase. The dispersion of the water-soluble antioxidant molecules is thus obtained by the clusters of phyllosilicate sheets, water and the dispersing or surfactant which together constitute a supramolecular structure. The minimum content of water-soluble antioxidants indicated is such that below this, their effectiveness becomes insufficient. This content corresponds substantially to an equivalent of water-soluble vitamin relative to vitamin E, naturally present in oils.

[0022] Advantageously, the content of water-soluble antioxidant is between 0.125% and 50% by weight relative to the weight of the phyllosilicate particles, and preferably between 0.375% and 35% by weight relative to the weight of the phyllosilicate particles.

[0023] Beyond this value of 50%, it becomes difficult to dissolve them in the swelling water of the phyllosilicates. Indeed, the phyllosilicates are pre-swollen by water promoting their exfoliation, but also constituting the solubilization medium of the water-soluble antioxidants. The water thus present in the phyllosilicates advantageously represents up to 200% of the weight of phyllosilicates of the lipid phase (described below). Vitamin C, being a water-soluble antioxidant, effective for the protection of lipids, has a solubility constant in water of 33mg / ml, cannot represent more than 66% of the clays. Taking into account the water physisorbed on the surface (not available), it is preferable to limit the quantity of vitamins to 50% of the clays, i.e. 25mg / ml.

[0024] The water-soluble antioxidant may be chosen from the group of reducing salts, reducing enzymes, flavonoids, phenolic derivatives and water-soluble vitamins and combinations thereof. Preferably, the antioxidant of the composition is vitamin C.

[0025] Advantageously, the amphiphilic dispersing agent is chosen from the group of ethyl lauroyl arginate (LAE), cationic surfactants based on arginine with 16 carbons and more, phospholipids and combinations thereof.

[0026] Preferably, the dispersing or amphiphilic surface agent is a phosphoglyceride and very preferably a phosphatidyl choline and very very preferably- mainly lecithin.

[0027] Advantageously, the phyllosilicate sheets are smectite sheets and very preferably mainly montmorillonite sheets.

[0028] Preferably, the content of dispersing or surface agent in the composition is between 10% and 400% and very preferably between 20% and 200% by weight relative to the weight of the phyllosilicates.

[0029] Preferably, the water content of the composition is between 10% and 300% and very preferably between 20% and 200% by weight relative to the weight of the phyllosilicates.

[0030] The invention also relates to an emulsion with an aqueous phase and a lipid phase, in which the lipid phase is a composition as previously described.

[0031] In this composition in the form of an emulsion, the phyllosilicate particles have a dual role: to provide support and fine dispersion of the water-soluble antioxidants in the lipid phase but also the role of mineral emulsifying particles which can be used indifferently for the stabilization of direct (O / W) or inverse (W / O) emulsions as well as double emulsions (W / O / W).

[0032] According to one embodiment, the emulsion is a direct emulsion and the overall level of phyllosilicate in the lipid phase is greater than 0.5% by weight relative to the weight of said lipid phase, and preferably between 1% and 20% by weight.

[0033] In this embodiment, the viscosity of the lipid phase increases, in particular with the level of phyllosilicates, and this is favorable to obtaining a direct emulsion.

[0034] According to another embodiment, the emulsion is an inverse emulsion, and the overall phyllosilicate content in said lipid phase is less than 5% by weight relative to the weight of said lipid phase, and preferably between 0.005% and 2% by weight.

[0035] In this embodiment, the viscosity of the lipid phase decreases with the reduction in the level of phyllosilicates and this is favorable to obtaining an inverse emulsion.

[0036] The invention also relates to foods, premixes or food supplements in the form of modular stacked objects allowing protection against oxidation and controlled release of nutritive and / or physiologically active substances for monogastric species, with an aqueous phase and a lipid phase with liposoluble active components, such that the aqueous phase and the lipid phase are an emulsion as previously described.

[0037] According to a first embodiment, the foods, premixes or food supplements are such that the emulsion is a direct emulsion and such that the drops of the dispersed lipid phase have a biopolymer coating, preferably chosen from the group of chitosan, polylysine, and hyaluronic acid.

[0038] According to a second embodiment, the foods, premixes or food supplements comprise a core and a coating of the core and are such that the core comprises the aqueous phase and the lipid phase and such that the aqueous phase comprises water-soluble active substances.

[0039] In this embodiment, the aqueous phase may be dispersed in the continuous lipid phase. The lipid phase may also be dispersed in the continuous aqueous phase, in the latter case, the aqueous phase is advantageously gelled.

[0040] The composition as previously described can also advantageously be incorporated or impregnated into an extruded food.

[0041] The invention also relates to the use of phyllosilicates as stabilizing agents for lipid emulsions.

[0042] These lipid emulsions comprise an aqueous phase and a lipid phase and the phyllosilicate particles introduced and dispersed in the lipid phase make it possible to stabilize these various and inverse emulsions.

[0043] The preceding elements or products have the advantage of comprising dispersed in the lipid phase hydrophilic antioxidants dispersed and stabilized by phyllosilicate particles. These antioxidants can reduce the deleterious effects of the oxidation of unsaturated lipids. The antioxidants are in fact more quickly attacked by reactive oxygen species, while remaining stable once oxidized, which allows the lipids not to be affected, or to delay the start of this oxidation, the excess antioxidant not consumed in the protection mechanism constitutes interesting nutritional contributions, with a delayed release into the digestive tract, this is an additional benefit to the proposed model of lipid stability implemented here. Description of Figures

[0044] The invention is described below with the aid of figures 1 to 16, given solely for illustration purposes:

[0045] [Fig-1] schematically presents a mechanism of oxidation of an unsaturated lipid;

[0046] [Fig.2] schematically illustrates a mechanism of regeneration of vitamin E by vitamin C (Guilland, 2011);

[0047] [Fig.3] shows a structural diagram of a bentonite;

[0048] [Fig.4] shows the formula of lecithin;

[0049] [Fig.5] schematically presents the evolution of the lecithin content as a function of the specific surface area of ​​the clay and for several coverage rates;

[0050] [Fig.6] shows a diagram of the evolution of the particle desorption energy in depending on their size;

[0051] [Fig.7] shows the phase diagram of the stability domains of the emulsions obtained by phyllosilicates;

[0052] [Fig-8] schematically shows the evolution of the size of the drops of the phase dispersed according to the size and concentration of the mineral particles;

[0053] [Fig.9] shows the size of mineral particles for two concentrations of clay;

[0054] [Fig. 10] shows the evolution of the size distribution of clay particles dispersed in a lipid phase during additional ultrasound (US) treatment;

[0055] [Fig. 11] shows the evolution of the size of the drops of the lipid phase as a function of the bentonite rate;

[0056] [Fig. 12] presents for two tests the size distributions of the mineral particles and oil drops as well as electron microscopy images of the emulsions;

[0057] [Fig. 13] shows the evolution of the measured peroxide index as a function of time;

[0058] [Fig. 14] shows a diagram of a first product;

[0059] [Fig. 15] shows a diagram of a second product; and

[0060] [Fig. 16] shows a diagram of a third product. Detailed description of the invention

[0061] The different constituent parts of the foods or food supplements according to one of the objects of the invention will be called “object” or “element”.

[0062] The term “product” will refer to foods and food supplements according to one of the objects of the invention, obtained by stacking the different objects.

[0063] By "gel" is meant a material that is primarily liquid, but behaves similarly to a solid due to a three-dimensional network entangled within the liquid. It is these entanglements that give gels their structure and properties. The three-dimensional network of solids diluted in the liquid may be the result of chemical or physical bonds, or of small crystals or other bonds that promote organization in the dispersion liquid.

[0064] An emulsion is of the “oil in water” type, when (i) the dispersing phase is an aqueous phase and (ii) the dispersed phase is an organic phase (hydrophobic, lipidic or oily). Such an emulsion is also commonly referred to as a “direct emulsion” or by the acronym “O / W”.

[0065] An emulsion is of the “water in oil” type, when (i) the dispersing phase is an organic phase (hydrophobic, lipidic or oily) and (ii) the dispersed phase is an aqueous phase. Such an emulsion is also commonly referred to as an “inverse emulsion” or by the acronym “W / O”.

[0066] We can also have so-called “double” emulsions, when an inverse emulsion is in turn dispersed in an aqueous phase. Such a double emulsion is a water-in-oil-in-water emulsion and is designated by the acronym “W / O / W”.

[0067] Supramolecular structures are structures or organizations obtained at the molecular scale, these organizations are obtained by non-covalent or weak interactions between atoms within a molecule or between molecules, within a molecular assembly. These molecular assemblies are nanometric-sized buildings, which can be organized on larger scales. These self-assemblies can give more complex buildings thanks to non-covalent interactions whose shape and size are governed by physicochemical interactions at the molecular scale.

[0068] In the context of the present invention, the term “labile” molecule is understood to mean a molecule bound to a substrate by physical, ionic interactions, or non-covalent Van der Waals forces, which gives them a capacity for reversible attachment or organization.

[0069] In the following, the D50 by volume of a particle sample represents the particle size for which 50% of the volume of the particles in the sample have a particle size less than this value (or greater). Composition according to the invention

[0070] The present invention thus relates to a composition comprising unsaturated lipids such as omega 3 and omega 6 and antioxidants. This composition is such that the antioxidants comprise water-soluble antioxidants stabilized by a supramolecular structure. The supramolecular structure comprises water and a self-organized amphiphilic dispersing agent adsorbed on the surface of clay sheets dispersed in the composition.

[0071] The supramolecular structure thus comprises the clay sheets, the water physisorbed between the sheets and the amphiphilic dispersing agent bound to the surface of the sheet clusters by ionic interaction, or Van der Waals bonds. Lipids

[0072] The lipids of the composition, whether hydrophobic, oily or organic, are chosen according to the applications envisaged from vegetable oils, mineral oils, synthetic oils, hydrophobic organic solvents and hydrophobic liquid polymers. The composition advantageously comprises unsaturated fatty acids, vitamins, antioxidants and essential oils.

[0073] In the examples, sunflower oil is used with or without cod liver oil. Antioxidants

[0074] The antioxidants of the composition according to one of the subjects of the invention comprise water-soluble antioxidants. These water-soluble antioxidants or protective molecules are preferably chosen from the group of reducing salts, such as Fe++, Cu+, etc., reducing enzymes, such as dismutases, oxidoreductases (such as laccases), flavonoids, phenolic derivatives (such as quercitins, isoflavones, anthocyanins, catechins, tannins, coumarins, etc.) and water-soluble vitamins. A preferentially used antioxidant is vitamin C. Water-soluble protective molecules have a dual role: a protective role with respect to lipids, but also as a beneficial nutritional contribution in the daily ration of food. The water-soluble antioxidant agent will be chosen to preferentially play the role of lipid protection agent. This is the case of vitamin C, which will be consumed (sacrificial molecule) in the presence of reactive oxygen, to delay the action of this oxygen on the unsaturations of lipids

[0075] It should be noted that oils naturally contain vitamin E in varying amounts. This fat-soluble vitamin E has a protective role against unsaturated lipids. [Fig.2] illustrates a mechanism for the regeneration of vitamin E by vitamin C. Vitamin E, in a first step, traps free radicals and forms a tocopheroxyl radical. Then vitamin C, in a second step, reduces this radical to regenerate it into α-tocopherol and generate an ascorbate radical.This is one of the plausible mechanisms of lipid protection, knowing that vitamin C also has the possibility of capturing the radical species of reactive oxygen, and thus reducing the probability of reaction with the unsaturations of lipids, in a last mechanism, vitamin C can also play the role of radical transfer agent towards vitamin E, which increases the effectiveness of vitamin E protection of lipids, and reduces the presence of peroxidized radicals on lipids, and therefore limits the propagation phase. Phyllosilicates

[0076] Phyllosilicates are clay minerals of the silicate group built by stacking tetrahedral ("T") layers where the tetrahedra share three out of four vertices (the "basal" oxygens), the fourth vertex (the "apical" oxygen) being connected to an octahedral ("O") layer occupied by different cations (Al, Mg, Fe, Ti, Li, etc.). [Fig.3] shows an example of a phyllosilicate structure. These stacked structures form organized sheets (as described in detail below) whose surface charge is negative over a wide pH range (4 <pH<9), qui seront stabilisés par des contres-ions cationiques. Ces contres-ions seront monovalents, ou divalents, ce qui confère à l’argile une capacité à être gonflée dans l’eau plus ou moins fortement, par insertion de molécules d’eau entre les feuillets.

[0077] Smectites are a group of clay minerals, and therefore silicates, more precisely phyllosilicates.

[0078] Their typical composition is A0JD2ÏT4OI0Z2.,, H2O, where A represents an interlayer cation (alkali or alkaline-earth element), D an octahedral cation, T a tetrahedral cation, O oxygen and Z a monovalent anion (generally OH-).

[0079] They crystallize in the monoclinic system.

[0080] These are phyllosilicates with a TOT (or 2:1) structure, i.e. made up of sheets comprising two head-to-tail tetrahedral layers, linked together by octahedral cations. The sheets are linked together by interlayer cations.

[0081] We distinguish between dioctahedral smectites (beidellite, montmorillonite, nontronite, etc.) and trioctahedral smectites (hectorite, saponite, etc.).

[0082] Montmorillonite is a 2 / 1 type clay, also called TOT (for tetrahedron / octahedron / tetrahedron). This means that a montmorillonite sheet is formed of three layers:

[0083] - an octahedral layer A1(OH )5O: 7 atoms for 6 vertices + aluminum at center. The OH and oxygen being shared between the different octahedra that make up the layer.

[0084] - and two tetrahedral layers which cover on each side the octahedral layer at its base; SiO4: 5 atoms for 4 vertices + silicon in the middle. The oxygens are shared between the different tetrahedra that make up the layer.

[0085] Imperfections in the crystal are compensated by interlayer cations, generally monovalent or divalent, which ensure the electrical neutrality of the mineral.

[0086] All phyllosilicates can be used, but smectites and particularly montmorillonites have the advantage, due to their lamellar structure with a greater spacing between the sheets than other phyllosilicates, of being able to be swollen by small molecules with hydrophobic properties which will improve the exfoliation of the clay platelets and thus facilitate their dispersion in the composition. Other phyllosilicates, but also micas and talcs can also be exfoliated in this way, but the energy which would be necessary to disperse the lamellar sheets in the lipid phase would be much higher.

[0087] In the examples, bentonite is used as phyllosilicate. Bentonites are clays mainly composed of montmorillonite, the interlayer cations of which are usually either calcium, sodium, potassium, their combination or other metal ions.

[0088] Bentonite is negatively charged on the surface (along the length) and positively charged on the sides (width) which allows it to interact with other charged molecules.

[0089] Clays are hydrophilic and smectites, including bentonite, have a swelling capacity. This characteristic allows water-soluble molecules to be adsorbed in the interlayer space of clays via an aqueous phase. Water is said to be physisorbed on the surface of the clay sheets via the silanol groups.

[0090] In the description, the term “clay” will also be used to refer to phyllosilicates. Dispersion or surfactant

[0091] A molecule with a hydrophobic part and a hydrophilic part is usually used as a dispersing or surfacing agent. The adhesion of this dispersing agent by physical interaction with the mineral particles makes it possible to make the clay sheets hydrophobic and to obtain good dispersion of these clay sheets in a lipid phase.

[0092] It is advantageous to use a dispersing agent having a cationic polar head and a hydrophobic chain, soluble in the lipid phase, such as phospholipids having cationic polar functions such as for serine, ethanolamine or choline, thus obtaining phosphatidylserine, phosphatidylethanolamine, or phosphatidylcholine, better known under the name of "lecithin". It is a lipid of the phosphoglyceride class. Arginine grafted onto a long alkyl chain (Cl6 and more) can also play this role of dispersing agent. Ethyl lauroyl arginate (LAE) can also be used.

[0093] All these dispersing agents are labile because they bind to the surface of the phyllosilicate sheet clusters by non-covalent interactions, which gives them a reversible attachment or organization capacity.

[0094] Phosphatidylcholine has ([Fig.4]):

[0095] - a hydrophilic pole: choline (1) and the phosphate group (2);

[0096] - a hydrophobic tail: fatty acid residues (here, the acid residues palmitic (5) and oleic (4)); and

[0097] - glycerol (3) links these two hydrophilic and hydrophobic poles.

[0098] The phosphate group is negatively charged, while choline is positively charged. Phosphatidylcholine is therefore zwitterionic.

[0099] It is both hydrophilic and lipophilic, and its hydrophilic-lipophilic balance (HLB) can vary between 2 and 9.5 depending on the fatty acid residues of the hydrophobic tail.

[0100] Dispersion / exfoliation of clay, especially bentonite, in oil

[0101] The objective of this step is to obtain the composition according to one of the objects of the invention.

[0102] To combine two systems which originally have no affinity, one apolar (lipids) and the other polar (aqueous phase + clay + water-soluble antioxidants), we will:

[0103] (1) Dissolve the soluble antioxidant(s) in water;

[0104] (2) Add the dispersing agent and obtain a homogeneous mixture;

[0105] (3) Add the clay and shear the resulting composition to pre-swell the sheets of phyllosilicate by swelling in water, and adsorb the dispersing agent to the surface of phyllosilicate particles, to make it compatible with the lipid phase;

[0106] (4) Add the lipids;

[0107] (5) Providing shear energy to the resulting composition to disperse / exfoliate the clay sheets in the lipid phase.

[0108] Steps (1) and (2) are obtained by adding water in sufficient quantity to solubilize the antioxidants and impregnate the clay sheets. It is advantageous to use between 1% and 40% by weight of water relative to the weight of the complete lipid phase, and preferably between 4 and 25%.

[0109] Clays are known for their water-absorbing properties, and they can swell, depending on their chemical and structural composition, between 2 times their mass in water, up to 20 times their mass in water. The clays thus swollen form a gel whose more or less swollen and more or less exfoliated layers integrate the entire volume of water. It is not necessary to saturate the entire water-absorbing capacity of the clays to obtain a satisfactory dispersion of the clay in the lipid phase, which is why we limit the water supply to 300% by weight relative to the clay. Conversely, it is necessary for the clays to be minimally impregnated with water to promote their dispersion. Exfoliable clays are usually stored at a humidity level of 10%. It is essential not to fall below the 5% threshold to avoid the collapse of the phyllosilicate sheets, leading to a structure which loses its exfoliation capacity.

[0110] Insufficient water content does not allow the solubilization of the molecules of interest.

[0111] When there is too high a water content, the clay sheets are easier to exfoliate but they are impregnated with water and they have less capacity to adsorb lecithin molecules. There is no possibility of formation of a supra-molecular structure necessary for the effectiveness of the protection.

[0112] Step (3) is obtained by using a dispersing agent, such as lecithin as a dispersing / exfoliating agent. This will adsorb onto the surface of the clay sheets by ionic interaction between the polar head of the lecithin and the silanol groups of the clays. The lecithin is pre-dissolved in the water from step (1) to facilitate its incorporation. The amount of lecithin can vary between a clay surface coverage rate of 5% and 100%. This coverage rate is calculated based on the total external clay surface after exfoliation, and the number of anionic charges on the surface of the sheets (usually there are around five silanol functions per nanometer squared, 5 / nm2) accessible by the lecithin (most swollen sheets (separated by water)). It therefore depends on the specific surface area of ​​the clay accessible by the dispersing agent.

[0113] It is therefore necessary to work on different rates of dispersing agent, depending on the clays used, which will have quantities of silanols sufficiently accessible to the lecithin molecules. It is necessary to aim for optimal coverage rates between 20% and 60% of the surface silanols of the particles depending on the particle size and the desired hydrophobation. Thus different types of particles can be prepared to stabilize direct or inverse emulsions.

[0114] [Fig.5] schematically presents the evolution of the necessary lecithin content by weight relative to the clay content by weight as a function of the specific surface area of ​​the exfoliated clays for several rates of coverage of the silanols of the clay sheets by lecithin.

[0115] This figure shows that the optimal lecithin content to obtain good exfoliation followed by stable direct or inverse emulsification is between 13% and 129% by mass relative to the mass of the clay for a coverage rate of 20% and respectively a specific clay surface area of ​​100 m2 / g and 1000 m2 / g. For a coverage rate of 60% the optimal lecithin content is between 39% and 387% by mass relative to the mass of the clay and respectively a specific clay surface area of ​​100 m2 / g and 1000 m2 / g.

[0116] When the content of dispersing agent such as lecithin is insufficient, the hydrophobic character of the clay particles is insufficient.

[0117] When the amount of dispersing agent such as lecithin allows the surface silanols of the particles to be covered, the dispersion of the clays in the lipid phase is promoted. At coverage rates close to 100%, the hydrophilic character is lost, which gives excellent stability of the clay particles in the lipids.

[0118] There is a competition between the dispersing agent such as lecithin and the water molecules for physisorption at the surface of the clays, therefore an excess of lecithin will be unfavorable to the amount of adsorbable water and consequently to the amount of antioxidant molecules stabilized at the clay-lipid interface in the composition.

[0119] For the bentonite used, with a specific surface area of ​​the order of 300 m2 / g, we must therefore have an optimal lecithin content of the order of 30 to 130% by weight relative to the mass of the clay with a coverage rate of between 20 and 60% of the surface silanols of the clay.

[0120] Step (5) can be obtained by shearing applied in batch using, for example, a Silverson (rotor-stator shear), additional treatment by ultrasound or using a high-pressure homogenizer is also possible to reduce the particle size. Process for obtaining the emulsion

[0121] To stabilize emulsions, one approach consists of using compounds called “emulsifiers” or “emulsifiers”.

[0122] These emulsifying compounds are most often emulsifying surfactants (also called “surface agents”) which, thanks to their amphiphilic structure, are placed at the oil / water interface and stabilize the dispersed droplets.

[0123] However, emulsifying compounds of this type do not always offer the desired stability over time, with a permanent balance of surfactants between the interface to be stabilized and the micelles in solution. In addition, synthetic surfactants often have ecological or food disadvantages, because they disrupt biological systems through strong interaction with cell membranes.

[0124] These emulsifying / emulsifying compounds can also consist of solid particles, which allow the production of emulsions called “Pickering emulsions”.

[0125] Pickering emulsions are emulsions, which are stabilized by colloidal particles suspended in the aqueous phase which become anchored at the oil / water interface interpreted as a wetting effect at the interface of the two phases, with high stability.

[0126] Unlike surfactants which adsorb and desorb continuously under the effect of thermal agitation, particles in colloidal suspension adsorb strongly at interfaces and the desorption energy of the particles as illustrated in [Fig.6] becomes high enough to make the phenomenon irreversible.

[0127] The phyllosilicate particles thus have an emulsifying role to stabilize the emulsions according to an object of the invention. These emulsions are thus Pickering emulsions.

[0128] The objective of this step is to obtain a stable emulsion with a dispersed phase in the form of drops in a continuous phase. The lipid phase comprises the dispersion of phyllosilicates in oil previously described. The aqueous phase is composed of water which can be supplemented by a monovalent salt, with a concentration between 0 and 100 mM in water, advantageously with NaCl at a concentration lower than 50 mM and very advantageously 25 mM. This ionic strength was chosen to limit the electrostatic repulsions due to the surface charges of the clay particles. To disperse the two immiscible phases, a shear energy will be applied in batch, at room temperature, with for example a rotor / stator device with an air gap of 150 micrometers with a 30 mm rotor, at 4500 rpm for 4 min

[0129] To obtain an emulsion according to one of the objects of the invention, a lipid phase is always used in which clay particles are dispersed and stabilized with a dispersing or surface agent in the presence of water as previously described.

[0130] The direct or inverse character of the emulsion obtained is mainly a function of the relative viscosities of the continuous phase and the dispersed phase, of the proportion of dispersed phase (less than 30% by weight) compared to the continuous phase at the start of the emulsification, knowing that the dispersed phase can then be added drop by drop to increase the proportion, it is thus possible to produce emulsions with more than 65% by weight of dispersed phase.

[0131] [Fig.7] shows the areas in which direct and inverse emulsions are mainly obtained as a function of the weight concentration of clays in the lipid phase on the abscissa and the viscosity ratio of the continuous and dispersed phases on the ordinate. Of course, this figure is only a diagram and other factors may intervene, for example the ratio of the weights of water and oil.

[0132] When the concentration of mineral particles in the lipid phase is low, less than 1% by weight relative to the weight of the lipid phase, the viscosity of the lipid phase decreases and the ratio of the viscosities of the two phases increases, approaches 1 and above and the conditions are favorable for obtaining inverse emulsions.

[0133] On the other hand, when the concentration of mineral particles in the lipid phase is high, greater than 5% by weight relative to the weight of the lipid phase, the viscosity of the lipid phase increases and the ratio of the viscosities of the two phases decreases. These conditions are favorable for obtaining direct emulsions.

[0134] The size of the drops of the dispersed phase obtained is a function of the size of the clay particles and the concentration of these clay particles. [Fig.8] schematically presents the observed changes.

[0135] For a given clay particle size, the drop diameter decreases with concentration; the more particles are used, the more interfaces they can stabilize and therefore the result is dispersed phase drops with smaller diameters. However, the size of the clay particles will impose a minimum drop size; the drops cannot be made smaller than the stabilizing particles.

[0136] It should be noted that the stabilization of emulsion drops by clay particles induces a stiffening of the interface with drops which lose their sphericity. Furthermore, the limit size of drops observed on the plateau with high clay concentration depends on the shear energy provided to fragment the drops.

[0137] Lipid Dispersion Particle Size Measurements (LDS)

[0138] The size of mineral particles obtained in a lipid medium is measured by dynamic light scattering (DLS). The experiments were carried out with a Malvem NanoZS instrument. All measurements were carried out at a temperature of 20 °C with a detection angle of 173 °. The The hydrodynamic diameter was obtained from the analysis of the correlation function using Malvem DTS software, and by approximating a spherical shape of the particles or clusters of phyllosilicate sheets by taking into account the largest dimensions of the particles. The viscosity of sunflower oil is 66 cSt.

[0139] The tested sample is brought by dilution to a concentration of 0.1% by weight of particles relative to the weight of the medium (water or oil). 1 min before the measurement, the tested sample is stirred with a vortex.

[0140] The figures presented give the evolution of the number of particles as a function of their size in semi-logarithmic coordinates.

[0141] Measurements of the size of drops of a direct or inverse emulsion (granulometer)

[0142] The average individual droplet diameters were measured by scattering laser light using a Horiba LA-960 particle size distribution analyzer (Kyoto, Japan). An analysis model was used with a refractive index of 1.54 and 1.33 for oil and water, respectively. Calibration of water as a reference was performed before each measurement. All emulsions were measured in a transmittance range of 80–90%. Measurements were routinely performed in triplicate. The diameter was expressed as the number-average diameter. Examples

[0143] Preparation of a dispersion of phyllosilicates, in particular bentonite, in sunflower oil

[0144] Dispersions of exfoliated bentonite particles with lecithin and water are prepared, according to the principles described above, in sunflower oil at bentonite concentrations of 0.5 to 15% by weight relative to the weight of the lipid or oily phase as previously indicated. The lecithin content is 64% by weight and the water content is 120% by weight relative to the weight of bentonite in the composition. The size of the mineral particles obtained is measured as previously indicated by dynamic light scattering.

[0145] [Fig.9] shows the result of particle size measurements of bentonite dispersed in the lipid phase for two mass concentrations of bentonite: 1% and 10%. At a concentration of 1%, the size distribution is monodisperse and has a maximum around 1 micrometer. At a concentration of 10%, a first particle peak is observed around 40 nanometers and a second around 900 nanometers. The increase in concentration for a given shear energy leads to a decrease in particle size which reflects an improvement in dispersion.

[0146] [Fig. 10] shows the evolution of the size distribution of clay particles dispersed in a lipid phase with and without additional ultrasonic dispersive treatment. The clay content in the lipid phase is 1% by weight relative to the weight of the lipid phase.

[0147] The additional ultrasound treatment results in the appearance of a size distribution peak of approximately 150 nm. As initially, there is a size distribution peak of approximately 1 micrometer. The additional ultrasound treatment must therefore improve the dispersion of the clay particles in the lipid phase with a very significant reduction in the size of a significant portion of the particles.

[0148] Preparation of a direct emulsion

[0149] Direct emulsions were prepared using an oil phase / aqueous phase ratio of 40 / 60. Emulsification was carried out by supplying shear energy applied in batch, at room temperature, with a rotor / stator device with a 150 micrometer air gap with a 30 mm rotor, at 4,500 rpm for 4 minutes.

[0150] The average diameter of the lipid drops of the dispersed phase of the direct emulsions was measured for all clay concentrations with a granulometer. [Fig. 11] presents the results obtained.

[0151] At low concentrations, the amount of bentonite is too low to stabilize the small drops, so they coalesce to create large drops, thus reducing the total interface surface area of ​​the system to be stabilized. This limited coalescence process is typical of Pickering emulsions and is characterized by a sharp decrease in droplet diameter at low concentrations.

[0152] At higher concentrations, the droplet diameter stops decreasing and stabilizes around 20 μm. In this range, the droplet diameter is stable while the amount of bentonite increases. This can be attributed to the ability of the sheets to orient themselves cooperatively. The bentonite sheets align by inducing a densification of the clay layer at the droplet interface without variation in diameter.

[0153] The interfacial stabilization properties of the clays were evaluated by a stability test consisting of centrifugation at 10,000 g for 5 min. This test accelerated the natural creaming process due to different densities (oil density is lower than water) and led to a concentrated emulsion under tight constraint conditions. Thus, the drops are in contact, forcing coalescence when the interface is unstable or when the surface coverage is insufficient. The emulsions with the lowest clay concentration are unstable, however this instability results from a lack of particles at the interface rather than from inefficient adsorption. The rest of the emulsions are stable to the test. In addition, the size of the drops was measured to verify their mechanical strength. No variation in size and size distribution is observed after centrifugation. Thus, the emulsions exhibit excellent mechanical resistance to deformation and coalescence. The dotted curve in [Fig. 11] is practically identical to the solid curve and thus the droplet diameter is the same before and after the 10,000 g centrifugation test.

[0154] [Fig. 12] illustrates the relationship between the size of bentonite particles dispersed in oil and the size of the oil drops in the dispersed phase. For a bentonite particle size of 473 nanometers, assessed by the D50 parameter in volume, the size of the oil drops is D50 = 40 micrometers. The size ratio is 85. For a particle size of 164 nanometers, the size of the drops is 20 micrometers. The size ratio is 122. This confirms that the finer the particle size, the smaller the size of the drops in the dispersed phase. A ratio between 80 and 130 is observed. This figure also shows electron microscopy images of the emulsions obtained. Tests

[0155] Several tests were carried out to show the interest of the previous composition in reinforcing the resistance to oxidation of lipid compositions. Clay exfoliation protocol in oil

[0156] First, the vitamin C is mixed with a spatula in the distilled water until it is completely dissolved.

[0157] Then the lecithin is added and stirred vigorously until a homogeneous mixture is obtained (the lecithin forms vesicles with the aqueous environment).

[0158] Then, the clay is added and mixed for 2x15 seconds in a blade disperser at 3,500 rpm. The water and vitamin C are placed between the clay sheets and pre-swell it. The lecithin, for its part, will be placed on the surface of the sheets, which will make the clays “hydrophobic” and therefore help their dispersion in the oil, and, on the other hand, allow the intercalation of the lecithin between the clay sheets to facilitate exfoliation, that is to say the dispersion of the clays in the oil.

[0159] Leave to rest for 15 minutes (to optimize the pre-swelling phase) then mix again for 15 seconds.

[0160] Finally, sunflower oil is added, then blended for 2 x 30 seconds with a blade mixer (at 3,500 rpm) to initiate the exfoliation of the clays in the oil. Then cod liver oil and vitamin E are added and blended for 2 x 30 seconds again.

[0161] This pre-exfoliated system is then passed to the rotor / stator with a 150 micrometer air gap and a 30 mm rotor at 4,000 rpm for 3 minutes to maximize exfoliation of the clays in the oil.

[0162] In the tests described below, all samples including references without clay and lecithin-free followed the same protocol.

[0163] Tests for evaluating the oxidative stability of lipid compositions

[0164] Table 1 shows the formulations of three oily reference samples.

[0165] [Tables 1] 1 Oil WO vite G VitE G 2 9£i R 0 ? 3 99 3 0,. 5

[0166] Table 2 shows the formulations of two samples comprising clay. All formulations are in mass percentage relative to the total mass of the sample.

[0167] [Tables2] Clay Lecithin Water VitE VitC Oil 4 4 0.73 16 0.2 0 79.07 5 4 0.73 16 0.2 0.5 78.57

[0168] The clay used is bentonite: Oscorna company (Ulm, Germany); the Lecithin is from Seah International (Wimille, France); Vitamin E: Roth (Karlsruhe, Germany); Vitamin C: meszépices (Dierrey Saint Pierre, France).

[0169] The samples were incubated under ambient atmospheric conditions, protected from light, but at a temperature of 37°C to accelerate oxidation kinetics. Samples were taken regularly for seven weeks.

[0170] The peroxide indices were measured directly after the samples were taken by iodometry according to the NF EN ISO 27107 and NF EN ISO 3960 standards.

[0171] [Fig. 13] shows the kinetics of the peroxide indices for the five previous samples. On the abscissa are the days of sample collection and on the ordinate the peroxide index measured in meqO2 / kg of lipid phase. To facilitate reading, the kinetics of the three reference samples are presented in the form of a curve and those of the two samples 4 and 5 in the form of histograms.

[0172] In [Fig. 13], we see that after a latency period of a few days, the oxidation of the three reference samples starts on the 7th day and then increases more and more rapidly. The three references show similar oxidations, with a higher value for the reference comprising only vitamin E.

[0173] On the other hand, the oxidations of the two samples comprising a supra-structure molecular according to one of the objects of the invention are very clearly lower.

[0174] It can be concluded that the presence of clay sheet particles dispersed in the composition makes it possible to limit the diffusion of reactive oxygen molecules by a barrier effect.

[0175] Between samples 4 and 5, a very marked difference is also noted, particularly during the first thirty days of the test. The presence of the antioxidant, vitamin C, dispersed by adsorption on the particles of the supramolecular structure, provides a latency period of around thirty days before the development of significant oxidation of the composition.

[0176] The peroxide index value of 15 is usually used as a limit not to be exceeded for human food products.

[0177] This index is exceeded for the three reference samples and for sample 4 comprising only vitamin E after approximately one week. On the other hand, this index is only reached for sample 5 comprising the molecular structure and vitamin C according to one of the objects of the invention after 32 days. This result illustrates the very great interest of the supramolecular structure to serve as a vehicle for vitamin C to protect lipid compositions from oxidation.

[0178] Food or food supplement with direct emulsion included in a hydrophilic matrix

[0179] [Fig. 14] shows schematically and in section without any respect for the respective dimensions of each phase a first example of food or food supplement obtained with a direct emulsion according to one of the objects of the invention.

[0180] This product 10 comprises a core 12 and a coating 14 of the core. The core 12 comprises a lipid phase in the form of stabilized spherical particles 18 dispersed in a hydrophilic matrix 16. It is a direct emulsion introduced into this matrix.

[0181] A first element or object of this product 10 is the presence of lipid particles 18 dispersed in the hydrophilic phase or matrix 16. These lipid particles 18 comprise mineral particles, phyllosilicates and preferentially smectites and very preferentially comprise mainly montmorillonites.

[0182] The lipid particles 18 also comprise a dispersing agent based on lipids or phospholipids with a cationic head, and preferably choline, a preferred example of dispersing agent is lecithin. These dispersing agents combined with water make it possible to solubilize antioxidants such as vitamin C and to form a supramolecular structure as previously described. These dispersing agents also make it possible to obtain good exfoliation and dispersion of the mineral particles in the lipid phase, prior to or simultaneously with the production of the direct oil / water emulsion. The mineral particles allow in particular when producing the oil / water emulsion, to stabilize the size of the lipid particles 18 when preparing foods or food supplements 10, but also to significantly reduce the migration of nutrients and physiologically active substances between the two lipid and hydrophilic phases 16, as well as the migration of pro-oxidant agents such as O2 radicals.

[0183] According to preferred embodiments, the lipid particles 18 are of substantially spherical shape and of diameter between 1 and 100 μm, and preferably between 5 and 20 microns.

[0184] The lipid particles 18 can advantageously comprise polyunsaturated fatty acids, vitamins and antioxidants, essential oils.

[0185] The lipid particles 18 comprise one or more vegetable or animal oils preferably chosen from oils having a high content of omega 6 and omega 3. Preferably, these lipid particles 16 comprise a high content of omega 6 and omega 3, in particular of the DHA and EPA types. The omega 3 content is preferably greater than 2% by weight relative to the weight of the lipid phase, i.e. of the lipid particles 18.

[0186] A second element or object of the product 10 is to comprise an aqueous phase 16 containing water-soluble nutritive or active substances, and gelling agents.

[0187] The terms “aqueous phase”, “hydrophilic matrix” and “aqueous matrix” will be used interchangeably.

[0188] Advantageously, the aqueous matrix 16 has a substantially spherical shape or not depending on the manufacturing method and has a diameter of less than 5 mm and preferably between 10 and 1000 μm.

[0189] The gelling of the aqueous phase 16 makes it possible to limit the leakage of nutrients and active substances to the outside when it is immersed in an aqueous medium.

[0190] To obtain this gelation, the aqueous phase 16 may advantageously comprise a neutral or functionalized polysaccharide with at least one function chosen from the carboxylic, sulfonate, alcoholate or phosphate functions, and preferably the carboxylic function with a content of between 1 and 8% by weight, preferably between 1 and 5.5% by weight relative to the total weight of a dry extract of the aqueous phase 18.

[0191] Advantageously, the aqueous phase 16 is gelled (crosslinked) by reaction of the polysaccharide with reagents such as multivalent cations in the presence of pyrophosphate or deltagluconolactone, by release of acid protons by aqueous hydrolysis, then solubilization (release) of the multivalent cations.

[0192] Preferably, the multivalent cations are chosen from the group of calcium, magnesium, zinc cations and their combinations.

[0193] Advantageously, the multivalent cation is a calcium salt chosen from the group of carbonate, sulfate, lactate, citrate, tartrate, caseinate and stearate.

[0194] According to a preferred embodiment, the emulsion of lipid particles 18 dispersed in the aqueous phase 16 comprises specific proteins or biopolymers intended to modify the properties of the interfaces between the lipid particles 18 and the aqueous phase 16. These properties can be permeability, electrostatic surface charges, surface tension, chemical functions, roughness, etc.

[0195] The molecular mass and pKi of these proteins or biopolymers can be selection criteria. For example, BSA (Bovine Serum Albumin) proteins can be used, the molecular mass of which is around 66 kDa and the pKi of 5.2; lysozyme proteins with a molecular mass of around 14 kDa and a pKi of 11.35 can also be used. Biopolymers such as chitosan, with a molecular mass that can vary from 75 kDa to 500 kDa, can also be used. These macromolecules are added to the aqueous phase 18 after the establishment of the so-called Pickering lipid emulsion.

[0196] The gelled aqueous phase 16 also optionally comprises an exfoliated mineral filler with a specific surface area greater than 100 m2 / g, advantageously between 200 and 500 m2 / g,

[0197] This mineral filler can be chosen from the group of phyllosilicates, and preferably the phyllosilicate is a smectite.

[0198] Preferably, the content of the lipid phase dispersed in the aqueous matrix 16 is between 5 and 70% by volume, and preferably between 10 and 20% by volume for complete foods and between 45 and 70% for food supplements, relative to the total volume of the core 12.

[0199] Below 5% by volume, the volume of the lipid phase is no longer sufficient to easily introduce the liposoluble active substances and have good homogeneity of composition of the cores 12 of the products 10.

[0200] Beyond 70%, it becomes much more difficult to maintain an oil emulsion dispersed in the aqueous phase 16 (the matrix no longer retains the emulsion drops, because the gel mesh is too weak).

[0201] The gelled aqueous phase 16 may comprise hydrophilic active substances such as proteins, amino acids, vitamins, prebiotics, probiotics, antioxidants, and combinations thereof.

[0202] Advantageously, the aqueous phase 16 further comprises an osmotic agent.

[0203] This osmotic agent can be chosen from the group of sugars, salts, water-soluble polymers preferably with a molecular mass of less than 150 kg / mole and combinations thereof.

[0204] A preferred choice of osmotic agent may be sorbitol with an in less than 5% by weight relative to the weight of the aqueous solution, i.e. of the aqueous phase 18 (in its complete formulation) so as not to make the final product indigestible. A content between 0.8 and 1.5% by weight of sorbitol is optimal. Guérande salt can also be used advantageously, which also provides useful mineral salts.

[0205] The third element of this product 10 is to comprise a coating 14 of the core 12.

[0206] Advantageously, the core 12 comprises free charges on the surface, the coating 14 of the core 12 comprises n layers C of biocompatible materials M+ and M- with a digestive system, in particular biopolymers, having an alternating stack of positive and negative electrostatic charges which form coacervates structured in a stack of layers, and n is at least equal to 1.

[0207] This coating 14 may comprise n layers C of biocompatible materials M+ and M-, in particular biopolymers, with an alternating stack of positive and negative electrostatic charges which form crosslinked coacervates structured in a stack of layers, being at least equal to 2.

[0208] This coating system 14 has the advantage of facilitating the modulation of the thickness of the coating layer 14 and the wide choice of biocompatible materials, in particular biopolymers, M+ and M-, makes it possible to modulate the mesh of biocompatible materials, in particular biopolymers, M+ and M-, on the surface, which is also stiffened by more or less strong crosslinks of this mesh. Modulating the stiffness of the coating 14 makes it possible to modulate the release of nutritive and / or physiologically active substances: the denser the stiffening, the smaller the mesh of biopolymers and the slower the release. This type of coating 14 crosslinked and structured in multilayers C also makes it possible to obtain a structural stability necessary for the preservation of the food 10 until its consumption and the release of nutritive and / or physiologically active substances, and in particular necessary for its handling.

[0209] This product 10 has strong potential in the effective substitution of live prey in hatcheries of marine fish species, as well as for shrimp nurseries. It also has strong interest for the supplementation of drinking water in monogastric farms such as poultry farms.

[0210] This product illustrated in [Fig. 14] can be produced as follows. A direct H / W emulsion is prepared, stabilized by the bentonite particles dispersed in the oily phase. Then, after gelling of the aqueous phase, the cores 12 can easily be obtained by mechanical cutting. It is also possible to produce a double water-in-oil-in-water emulsion stabilized by gelling of the aqueous phase and recover the cores 12 by separation between the oil phase and the washing water, for example by centrifugation. The coating 14 is then produced.

[0211] Lipid product with rigid interface particles from direct emulsion

[0212] [Fig. 15] shows a lipid product 20 which is a direct application of a composition according to one of the objects of the invention in the form of a direct H / W emulsion.

[0213] We see the lipid particles 28 surrounded by a coating 24 and dispersed in an aqueous phase 26.

[0214] The lipid particles or drops, which comprise a supramolecular structure as previously described, are also stabilized by the dispersed phyllosilicate mineral particles. They are advantageously coated after they have been obtained. This coating is intended to make them more mechanically robust by tolerating deformation without breaking; it also limits the risks of leaching of the contents of the lipid drops into the aqueous phase. This coating can advantageously be chitosan, polylysine, or hyaluronic acid.

[0215] This lipid product is obtained from a direct oil / water emulsion obtained by dispersing in water a composition as previously described. The emulsion can be concentrated by separation of the aqueous phase, this separation can be carried out by any means, in particular by centrifugation.

[0216] The lipid particles preferably have a size of the order of 1 to 20 micrometers. This very small size gives them good mechanical resistance. With a chitosan coating, these lipid particles can in particular be used to provide a lipid phase for direct use (food for zooplankton) or by incorporation into food premixes or food supplements, even when these are obtained by an extrusion process.

[0217] Advantageously, this emulsion can be a double emulsion to provide sensitive water-soluble nutrients such as prebiotics, enzymes, antioxidants, vitamins, or peptides.

[0218] Food or food supplement with a rigid interface resulting from a double emulsion

[0219] [Fig. 16] shows a third food or food supplement obtained using a composition according to one of the objects of the invention in the form of a W / O / W double emulsion.

[0220] This product 30 comprises a core 32 and a coating 34 of the core. The core 32 comprises an aqueous phase in the form of spherical (or irregular) particles 36, the particles 36 are dispersed in a lipid matrix 38. It is an inverse emulsion.

[0221] A first element or object of this third product is that it contains an optionally gelled aqueous phase containing water-soluble active substances, including in particular nutrients.

[0222] Advantageously, the size of the aqueous particles 36 is between 0.1 and 50 micrometers and preferably between 0.5 and 20 micrometers.

[0223] Advantageously, the aqueous particles 36 are stabilized by the phyllosilicates dispersed in the lipid phase.

[0224] Advantageously, an optional gelling is applied to the aqueous phase, which makes it possible to limit the leakage of nutrients and active substances outside the particles 36. It also makes it possible to modulate the rate of release of the active substances it contains during the digestion phase.

[0225] Advantageously, the aqueous phase can be gelled by reaction of an anionic polysaccharide, advantageously carboxyl functionalized, with reagents such as a calcium salt as well as pyrophosphate or deltagluconolactone.

[0226] Advantageously, the aqueous phase may additionally comprise an osmotic agent. This may be chosen from the group of sugars, salts, water-soluble polymers preferably with a molecular mass of less than 150 kg / mole and combinations thereof.

[0227] Preferably, the content of the aqueous phase dispersed in the lipid matrix 38, and thus the content of optionally gelled particles 36, is between 10 and 50% by volume, and preferably between 15 and 30% by volume relative to the total volume of the aqueous phase and the lipid matrix 38, i.e. relative to the total volume of the core 32.

[0228] As in the case of the first food or food supplement described, the optionally gelled aqueous phase, and thus the optionally gelled particles 36, may comprise hydrophilic active substances such as amino acids, vitamins, prebiotics, enzymes, probiotics, mineral salts, antioxidants, and combinations thereof.

[0229] A second element or object of this third product 30 is that the aqueous phase, i.e. the particles 36, is dispersed in a lipid matrix or phase 38.

[0230] Advantageously, the second object or element of the product 30, the lipid matrix 38, comprises a supramolecular structure as previously described. This lipid matrix comprises at least one vegetable or animal oil, in particular fish oil, water-soluble antioxidants, an exfoliated mineral filler, phyllosilicates and preferably smectites, and optionally at least one crystallizable wax. The mineral particles dispersed in the lipid matrix allow the stabilization of the particles 26 of the aqueous phase in the inverse emulsion.

[0231] Waxes can be of animal (beeswax) or vegetable origin.

[0232] According to preferred embodiments, the lipid matrix 28 is of substantially spherical shape and thus the core 32 is of substantially spherical shape and of diameter between 1 and 1000 μm and preferably between 5 and 400 μm.

[0233] The lipid matrix 38 can advantageously comprise vitamins.

[0234] Preferably, this lipid matrix 38 comprises a high content of omega 6 and omega 3, especially DHA and EPA types.

[0235] The lipid matrix 38 advantageously comprises at least 1% by weight of omega 3 of DHA and EPA types relative to the weight of the lipid matrix 18. It also preferably comprises less than 50% by weight of omega 3 of DHA and EPA types and very preferably less than 20% by weight relative to the weight of the lipid matrix 38.

[0236] According to an advantageous embodiment, the content of the mineral filler in the lipid matrix 38 is between 0.5 and 35% by weight and preferably less than 15% by weight, i.e. between 0.5% and 15% by weight, relative to the weight of the lipid matrix 38.

[0237] The third element or object of this third product 30 is to comprise a coating 34 around the core 32, of at least one layer of chitosan. This coating can advantageously be identical to that of the first product.

[0238] The core(s) 32 are prepared from a double water-in-oil-in-water emulsion. The coating 34 is then carried out, followed by filtration or decantation. Finally, drying is carried out to bring the moisture content of the products to a value lower than 10% by weight, relative to the total weight of the product 30. This last step is optional.

Claims

Claims

1. Lipid composition comprising unsaturated lipids such as omega 3 and omega 6, antioxidants, an amphiphilic dispersing agent and phyllosilicate particles, characterized in that the phyllosilicate particles are clusters of sheets in which water is absorbed, in that said antioxidants comprise water-soluble antioxidants dissolved in said water adsorbed in the phyllosilicate sheets at a content greater than 0.01% by weight relative to the weight of the lipids in the composition, and in that the phyllosilicate sheets are dispersed and exfoliated in the composition by said amphiphilic dispersing agent adsorbed on the surface of the phyllosilicate particles.

2. Composition according to claim 1, in which the content of water-soluble antioxidant is between 0.125% and 50% by weight relative to the weight of the phyllosilicate particles, and preferably between 0.375% and 35% by weight relative to the weight of the phyllosilicate particles.

3. Composition according to any one of the preceding claims, wherein said water-soluble antioxidant is chosen from the group of reducing salts, reducing enzymes, flavonoids, phenolic derivatives and water-soluble vitamins and combinations thereof, and preferably vitamin C.

4. A composition according to any preceding claim, wherein said amphiphilic dispersing agent is selected from the group of ethyl lauroyl arginate (LAE), cationic surfactants based on 16-carbon and higher arginine, phospholipids and combinations thereof.

5. The composition of claim 4, wherein said amphiphilic dispersing agent is a phosphoglyceride.

6. Composition according to claim 5, wherein said amphiphilic dispersing agent is a phosphatidyl choline and preferably lecithin.

7. Composition according to any one of the preceding claims, in which the phyllosilicate sheets are smectite sheets and very preferably predominantly montmorillonite sheets.

8. Composition according to any one of the preceding claims, in which the content of dispersing agent in the composition is between 10% and 400% and preferably between 20% and 200% by weight relative to the weight of the phyllosilicates.

9. Composition according to any one of the preceding claims, in which the water content of the composition is between 10% and 300% and preferably between 20% and 200% by weight relative to the weight of the phyllosilicates.

10. Emulsion with an aqueous phase and a lipid phase, characterized in that the lipid phase is a composition according to any one of the preceding claims.

11. An emulsion according to claim 10, wherein said emulsion is a direct emulsion and wherein the overall phyllosilicate content in said lipid phase is greater than 0.5% by weight relative to the weight of said lipid phase, and preferably between 1% and 20% by weight.

12. Emulsion according to claim 10 or 1, wherein said emulsion is an inverse emulsion, and wherein the overall phyllosilicate content in said lipid phase is less than 5% by weight relative to the weight of said lipid phase, and preferably between 0.005% and 2% by weight.

13. Food, premix or food supplement (10, 20, 30) in the form of modular stacked objects allowing protection against oxidation and controlled release of nutritive and / or physiologically active substances for monogastric species, with an aqueous phase (16, 26, 36) and a lipid phase (18, 28, 38) with liposoluble active components, characterized in that the aqueous phase and the lipid phase are an emulsion according to any one of claims 10 to 12.

14. Food, premix or food supplement (20) according to claim 13, wherein the emulsion is a direct emulsion and wherein the drops of the dispersed lipid phase (28) have a coating of biopolymer (24), preferably chosen from the group of chitosan, polylysine and hyaluronic acid.

15. A food, premix or food supplement (10, 30) according to claim 13, comprising a core (12, 32) and a coating (14, 34) of the core (12, 32), wherein said core (12, 32) comprises said aqueous phase (16, 36) and said lipid phase (18, 38) and wherein said aqueous phase comprises water-soluble active substances.

16. Use of a composition according to any one of claims 1 to 9, characterized in that said composition is incorporated or impregnated in an extruded food.

17. Use of exfoliated phyllosilicates in a lipid phase as stabilizing agents for lipid emulsions according to any one of claims 10 to 12.

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