WO2019129770A1 - Sulfated oligosaccharides and cosmetic uses thereof - Google Patents

Sulfated oligosaccharides and cosmetic uses thereof Download PDF

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Publication number
WO2019129770A1
WO2019129770A1 PCT/EP2018/086856 EP2018086856W WO2019129770A1 WO 2019129770 A1 WO2019129770 A1 WO 2019129770A1 EP 2018086856 W EP2018086856 W EP 2018086856W WO 2019129770 A1 WO2019129770 A1 WO 2019129770A1
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Prior art keywords
extract
weight
ulvan
relative
dry weight
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PCT/EP2018/086856
Other languages
French (fr)
Inventor
Lucie TOURNIER-COUTURIER
Yegor DOMANOV
Anne POTTER
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L'oreal
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Publication of WO2019129770A1 publication Critical patent/WO2019129770A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9706—Algae
    • A61K8/9722—Chlorophycota or Chlorophyta [green algae], e.g. Chlorella
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/007—Preparations for dry skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations

Definitions

  • the present invention relates to a particular extract of sulfated oligosaccharides, its production method and a method of cosmetic treatment of the skin using this extract.
  • the skin is a tissue whose cells are contiguous and integral with each other.
  • the cutaneous tissue forms an outer covering comprising sebaceous or sweat glands, and hair follicles.
  • the cutaneous tissues include the skin and the scalp, which are epitheliums with continual renewal. Renewal, or desquamation, is a coordinated and finely regulated process resulting in the elimination of surface cells, insensitively and nonvisibly.
  • the cutaneous tissue consists of two compartments namely a superficial compartment, the epidermis, and a deep compartment, the dermis.
  • the epidermis is conventionally divided into a basal layer of keratinocytes constituting the germinal layer of the epidermis, a so-called spinous layer consisting of several layers of polyhedral cells arranged on the germinal layers, one to three so-called granular layers consisting of flattened cells containing distinct cytoplasmic inclusions, keratohyaline grains and finally, a set of upper layers called horny layers (or stratum corneum), consisting of keratinocytes at the terminal stage of their differentiation called corneocytes.
  • Corneocytes are anucleate cells consisting primarily of a fibrous material containing cytokeratins, surrounded by a horny envelope. There is constantly production of new keratinocytes to compensate for the continuous loss of epidermal cells in the stratum corneum by a mechanism called desquamation.
  • Stratum corneum disorders can lead to fragility, even a lack of barrier properties of the epidermis, chronic dehydration of the stratum corneum, loss of mechanical elasticity, cutaneous discomfort and tightness.
  • an alteration of the skin barrier can occur in the presence of external aggressions as with detergents, acids, bases, oxidants, reducing agents, concentrated solvents, gases or harmful fumes, and / or following mechanical stress (friction, shock, abrasion, tearing of the surface, projection of dust, particles), and / or thermal or climatic imbalances (cold, dryness), or following psychological stress.
  • Patent application FR2982152 describes certain polysaccharides to improve the skin's barrier function, in particular to promote hydration. The application of these polysaccharides produces a sensation of comfort (absence of tightness of the skin).
  • oligosaccharides which promote the softness of the cutaneous tissues, in particular the stratum corneum and thus generate a feeling of comfort.
  • These oligosaccharides may in particular be obtained by specifically hydrolysing the ulvans described in the patent application FR2982152.
  • the present invention relates to an extract comprising at least one ulvan oligomer having a molecular weight between 5000 Da and 90 000 Da, and preferably between 15000 Da and 92 000 Da and more particularly between 16 000 Da and 85 000 Da.
  • the extract comprising at least one ulvan oligomer according to the invention has in particular two populations of different molecular weights, from 15,000 to 30,000 Da, in particular from 17,000 to 25,000 Da for the first population, hereinafter referred to as population A, and from 55000 to 90000 Da, in particular from 66000 to 80000 Da for the second population, hereinafter referred to as population B.
  • population A 15,000 to 30,000 Da
  • population B 17,000 to 25,000 Da
  • population B the mass ratio between the population A, comprising oligomers of lower molecular weight
  • the population B comprising oligomers of higher molecular weight
  • the invention also relates to a particularly cosmetic composition containing at least one ulvan oligomer as defined below and / or an extract according to the invention.
  • the subject of the invention is also a process for cosmetic treatment of the skin using at least one ulvan oligomer as defined below or at least an extract according to the invention or a composition according to the invention for softening and / or reducing the tightness of the skin.
  • Oligomers are understood to mean sulphated oligosaccharides preferably comprising between 25 and 500 monosaccharides and in particular between 90 and 150 monosaccharides.
  • Ulvans are sulphated anionic polysaccharides containing rhamnose obtained from green algae belonging to the order of the ulvals. Ulvans are water-soluble sulfated anionic polysaccharides that are localized in the cell wall. Ulvans are particularly extracted from ulvae or enteromorphs. These green algae are part of the phylum of chlorophytes and of the order of the ulvals characterized by a thallus in tube (enteromorphic) or double cell layer (ulve).
  • Ulvans account for 8 to 29% of the dry weight of algae. They consist mainly of rhamnose, glucuronic acid, glucose, galactose and xylose and also include sulphated groups. They may also include varying amounts of galacturonic acid, iduronic acid and mannose.
  • Rhamnose is generally sulphated at position 3.
  • Xylose may also be partially sulphated.
  • Most of the constituent sugars are distributed according to repetitive sequences.
  • the two major sequences are disaccharide sequences, one called ulvanobiuronic acid with 3 type A sulfates (A3s) comprising rhamnose 3-sulfate linked to glucuronic acid by a type 1 link 4, the other denominated 3-type ulvanobiuronic acid type B (B3s) comprising rhamnose 3-sulfate linked to iduronic acid by a type 1 linkage 4.
  • A3s ulvanobiuronic acid with 3 type A sulfates
  • B3s denominated 3-type ulvanobiuronic acid type B
  • the relative proportion of sugars varies according to the place of harvest of the ulva, the species and the time of harvest in the year.
  • the ulvan oligomers of the invention comprise rhamnose, glucuronic acid, iduronic acid, xylose, galactose and glucose.
  • the extract comprising at least one ulvan oligomer according to the invention has a content of sulphates grafted onto the oligomer (s) of ulvans of between 4 and 15%, more particularly between 6% and 12%, and preferably between 7 and 10%, in particular 7.5%, by weight relative to the dry weight of the extract.
  • the ulvan oligomer according to the invention is preferably from Ulva lactuca.
  • the extract comprising at least one ulvan oligomer according to the invention is preferably prepared from the green alga Ulva lactuca.
  • the extract comprising at least one ulvan oligomer according to the invention therefore preferably comes from Ulva lactuca.
  • the present invention also relates to an extract comprising at least one ulvan oligomer according to the invention.
  • the extract according to the invention comprises at least one ulvan oligomer having an average molecular weight between 5000 Da and 90 000 Da, preferably between 15 000 Da and 92 000 Da and more particularly between 16 000 Da and 85 000 da.
  • the extract according to the invention comprises at least one oligomer of ulvan (a) with a molecular weight of between 15,000 and 30,000 Da, in particular between 17,000 and 25,000 Da, and at least one ulvan oligomer. (b) of molecular weight between 55,000 and 90,000 Da in particular between 66,000 to 80,000 Da.
  • the total mass of ulvan oligomers of type (a) is greater than the total mass of ulvan oligomers of type (b).
  • the extract according to the invention does not comprise sulphated polysaccharides having a molecular weight greater than 250,000 Da and more particularly greater than 150,000 Da and preferably does not comprise sulphated polysaccharides having a molecular weight greater than 100,000 Da.
  • the average sulfation rate of the ulvan oligomer (s) is between 4 and 15%, more particularly between 6% and 12%, and preferably between 7 and 10%, by weight relative to the dry weight of the extract of the invention.
  • the average sulfation rate of the ulvan oligomer (s) is 7.5%.
  • the extract comprises proteins.
  • proteins When proteins are present, they preferably constitute from 0.01 to 15%, more particularly from 0.1% to 10%, more preferably from 1% to 8%, and especially from 2% to 5%, such as 2.95%. % by weight relative to the dry weight of the extract.
  • the oligomers of ulvans contained in the extract essentially comprise rhamnose and then, by decreasing masses, glucuronic acid in a quantity of the same order as iduronic acid, then in smaller amounts, xylose, galactose and glucose.
  • the oligomers of ulvans contained in the extract comprise from 20 to 30%, more particularly 24.4%, by weight of rhamnose relative to the dry weight of the extract.
  • the oligomers of ulvans contained in the extract comprise 5 to 15%, more preferably 8 to 12% and in particular 10.6% by weight of glucuronic acid relative to the dry weight of the 'extract.
  • the oligomers of ulvans contained in the extract comprise 5 to 15%, more preferably 10 to 15% and especially 12.1% by weight of iduronic acid relative to the dry weight of the extract.
  • the oligomers of ulvans contained in the extract comprise 1 to 10% by weight of each of the sugars among xylose, galactose and glucose relative to the dry weight of the extract.
  • the oligomers of ulvans contained in the extract comprise 1 to 10%, more particularly 3.5% by weight of xylose relative to the dry weight of the extract.
  • the oligomers of ulvans contained in the extract comprise 1 to 10%, more particularly 2.4% by weight of galactose relative to the dry weight of the extract.
  • the oligomers of ulvans contained in the extract comprise 1 to 10%, more particularly 5.7% by weight of glucose relative to the dry weight of the extract.
  • the oligomers of ulvans agreed in the extract comprise 20 to 30%, more particularly 24.4% by weight of rhamnose relative to the dry weight of the extract, 8 to 12% , more particularly 10.6% by weight of glucuronic acid relative to the dry weight of the extract, 10 to 15%, more particularly 12.1% by weight of iduronic acid relative to the dry weight of the extract, 1 at 10%, more particularly 3.5% by weight of xylose relative to the dry weight of the extract, 1 to 10%, more particularly 2.4% by weight of galactose relative to the dry weight of the extract and 1 at 10%, more particularly 5.7% by weight of glucose relative to the dry weight of the extract.
  • the extract according to the invention may further comprise mineral substances as defined below.
  • the extract according to the invention also comprises between 0 and 50% of mineral matter, more particularly between 5 and 40%, more particularly between 25 and 35% by weight, such as 30% or 30.1% by weight. weight relative to the dry weight of the extract.
  • drying can be carried out in a ventilated oven for 24 hours at 103 ° C.
  • the calcination can be carried out for 12 hours at 550 ° C.
  • the extraction of ulvans can be carried out from dried algae.
  • the extract according to the invention comprises between 50 and 100% of organic matter, more particularly between 60 and 95%, more particularly between 65 and 75% by weight, such as 70% or 66.9% by weight relative to to the dry weight of the extract.
  • the extract according to the invention comprises between 20 and 80% oligomer (s) of ulvan, more particularly between 25 and 60%, more preferably between 30 and 50% by weight, such as 40% by weight. relative to the dry weight of the extract.
  • oligomer (s) of ulvan more particularly between 25 and 60%, more preferably between 30 and 50% by weight, such as 40% by weight. relative to the dry weight of the extract.
  • the level of sulphate grafted on the ulvan oligomers of the extract is from 4 to 15%, more particularly from 6% to 12%, and preferably from 7 to 10%, such as than 7.5% by weight relative to the dry weight of the extract.
  • the level of free sulfate of the extract is from 0 to 20%, more particularly from 5% to 15%, and preferably from 8 to 14%, such as 1 1, 8%. by weight relative to the dry weight of the extract of the invention.
  • the sodium (Na) content of the extract is 10 to 15%, more particularly 1 1, 38% by weight relative to the dry weight of the extract.
  • the extract according to the invention comprises between 65 and 75%, more particularly 66.90% by weight of organic matter relative to the dry weight of the extract, 25 to 35%, more particularly 30.1% by weight of mineral matter relative to the dry weight of the extract, 10 to 15%, more particularly 1 1, 38% by weight of Na relative to the dry weight of the extract, 2 to 5 %, more particularly 2.95%, by weight of protein relative to the dry weight of the extract, 30 to 50%, more particularly 40%, by weight of total sugars (glucose equivalent) relative to the dry weight of the extract, 7 to 14%, more particularly 1 1, 8%, by weight of free sulfate relative to the dry weight of the extract, 7 to 10%, more particularly 7.5% by weight of grafted sulfate relative to the weight dry extract.
  • the extract according to the invention may be the new extract named by the Applicant "OligoUlvane”.
  • OIigoUlvane is produced from Ulva lactuca and contains oligomers of ulvans.
  • the oligomers of ulvans represent, in glucose equivalent, from 20 to 80%, more particularly from 25 to 60%, more preferably from 30 to 50% by weight, such as 40% by weight relative to dry weight of OligoUlvane extract.
  • the dry extract of OIigoUlvane comprises from 0 to 50% of mineral matter, more particularly from 5 to 40%, more preferably from 25 to 35% by weight, such as 30% or 30.1% by weight relative to the dry weight of OligoUlvane extract.
  • the dry extract of OIigoUlvane comprises between 50 and 100% of organic matter, more particularly between 60 and 95%, more particularly between 65 and 75% by weight, such as 70% or 66.9% by weight. weight relative to the dry weight of OligoUlvane extract.
  • the oligomers of ulvans have an average molecular weight between 5000 Da and 90 000 Da, preferably between 15 000 Da and 92 000 Da and more particularly between 16 000 Da and 85 000 Da.
  • the oligomers of ulvans included in the OligoUlvane extract as defined above are oligomers with a molecular weight ranging from 15,000 to 30,000 Da, in particular between 17,000 and 25,000 Da, and oligomers of molecular weight ranging from 55,000 to 90,000 Da, in particular from 66,000 to 80,000 Da.
  • the total mass of ulvan oligomers with a molecular weight ranging from 15,000 to 30,000 Da is greater than the total weight of molecular weight ulvan oligomers. ranging from 55,000 to 90,000 Da.
  • the level of sulphate grafted on the ulvan oligomers of the OligoUlvane extract is from 4 to 15%, more particularly from 6% to 12%, and preferably from 7 to 10%, such as 7.5% by weight based on the dry weight of the OligoUlvane extract of the invention.
  • the level of free sulphate of the OligoUlvane extract is from 0 to 20%, more particularly from 5% to 15%, and preferably from 8 to 14%, such as 1 1, 8 % by weight relative to the dry weight of the OligoUlvane extract of the invention.
  • the sodium (Na) content of the OligoUlvane extract is from 10 to 15%, more particularly from 1 to 38% by weight relative to the dry weight of the OligoUlvane extract. 'invention.
  • the OligoUlvane extract comprises proteins.
  • proteins When proteins are present, they preferably constitute from 0.01 to 15%, more particularly from 0.1% to 10%, more preferably from 1% to 8%, and especially from 2% to 5%, such as 2.95%. % by weight relative to the dry weight of the OligoUlvane extract of the invention.
  • the OligoUlvane extract comprises between 65 and 75%, more particularly 66.90% by weight of organic matter relative to the dry weight of the OligoUlvane extract of the invention, 25 to 35% by weight. %, more particularly 30.1% by weight of mineral matter relative to the dry weight of the OligoUlvane extract of the invention, 10 to 15%, more particularly 1 1, 38% by weight of Na relative to the dry weight of the OligoUlvane extract of the invention, 2 to 5%, more particularly 2.95%, by weight of proteins relative to the dry weight of the OligoUlvane extract of the invention, 30 to 50%, more particularly 40%, by weight of total sugars (glucose equivalent) relative to the dry weight of the OligoUlvane extract of the invention, 7 to 14%, more particularly 1 1, 8%, by weight of free sulfate relative to the dry weight of the OligoUlvane extract of the invention, 7 to 10%, more particularly 7.5% by weight of grafted sulf
  • the oligomers of ulvans contained in the OligoUlvane extract essentially comprise rhamnose, then, in descending masses, glucuronic acid in a quantity of the same order as iduronic acid, then in smaller amounts, xylose, galactose and glucose.
  • the oligomers of ulvans contained in the OligoUlvane extract comprise from 20 to 30%, more particularly 24.4% by weight of rhamnose relative to the dry weight of the OligoUlvane extract of the OligoUlvane extract. invention.
  • the oligomers of ulvans contained in the OligoUlvane extract comprise 5 to 15%, more preferably 8 to 12% and in particular 10.6% by weight of glucuronic acid relative to the dry weight of the OligoUlvane extract of the invention.
  • the oligomers of ulvans contained in the OligoUlvane extract comprise 5 to 15%, more preferably 10 to 15% and in particular 12.1% by weight of iduronic acid relative to the dry weight of the OligoUlvane extract of the invention.
  • the oligomers of ulvans contained in the OligoUlvane extract comprise 1 to 10% by weight of each of the sugars among xylose, galactose and glucose relative to the dry weight of the OligoUlvane extract. of the invention.
  • the oligomers of ulvans contained in the OligoUlvane extract comprise 1 to 10%, more particularly 3.5% by weight of xylose relative to the dry weight of the OligoUlvane extract of the invention. .
  • the oligomers of ulvans contained in the OligoUlvane extract comprise 1 to 10%, more particularly 2.4% by weight of galactose relative to the dry weight of the Oligoulvane extract of the invention. .
  • the oligomers of ulvans contained in the OligoUlvane extract comprise 1 to 10%, more particularly 5.7% by weight of glucose relative to the dry weight of the OligoUlvane extract of the invention.
  • the oligomers of ulvans agreed in the OligoUlvane extract comprise 20 to 30%, more particularly 24.4% by weight of rhamnose relative to the dry weight of the OligoUlvane extract of the OligoUlvane extract. 8 to 12%, more particularly 10.6% by weight of glucuronic acid relative to the dry weight of the OligoUlvane extract of the invention, 10 to 15%, more particularly 12.1% by weight of iduronic acid.
  • the contents of dry matter, mineral matter, and organic matter, as well as the sulphate and protein contents of the extracts comprising at least one ulvan oligomer as defined above, such as the OligoUlvane extract can be measured. according to the following methods:
  • the dry matter content (DM) corresponds to the weight obtained after drying of the raw material (MB) for 24 hours at 103 ° C .;
  • organic matter (OM) and mineral (MM) can be quantified by gravimetry after 12 hours at 550 ° C;
  • the sulphate content (SO 4 ) can be quantified according to Quemener et al. (Quemener, B., Lahaye, M., Bobin-Dubigeon, C. (1997) Sugar determination in a chemical-enzymatic method coupled to high performance anion exchange chromatography, Journal of Applied Phycology, 9, 179-188);
  • the protein content can be estimated from the N Kjelhdahl x 6.25 nitrogen assay;
  • the total content of uronic acids can be determined by colorimetric method, using m-phenyl phenol (Thibault J.-F. 1979. Automation of the dosage of pectic substances by the meta-hydroxydiphenyl method Lebensm-Wiss. echnol., 12, pp. 247-251.), using D-glucuronic acid as a standard;
  • the profile and content of neutral sugars and uronic acids can be determined by HPLC after acid methanolysis in MeOH-HCl (Absorbosphere RP18 column, 5 ⁇ m, 4 ⁇ 250 mm (according to Quemener et al, Food Hydrocolloids, 2000, 14, pp. Chromatographic peaks are identified by comparison with reference sugars.
  • the access to the composition is based firstly on a hot methanolysis, in order to break the existing glycosidic bonds between the saccharide and the uronic acids constituting the polysaccharide reaction leads to formation from 4 to 6 methyl glycosides per constituent sugar of the polymer.
  • These compounds are then identified and quantified by liquid phase chromatography, reverse phase on a C18 column. The identification and quantification are based on comparison to standards of monomeric uronic sugars and acids having undergone the same acid methanolysis treatment.
  • the molecular weight distribution profile (Mw) of ulvan oligomers in the extracts of the invention such as OligoUlvane can be established by steric exclusion HPLC chromatography (Shodex SB-806M HQ column, injection volume: 50 ⁇ L mobile phase: 0.05M NaNO3 + 0.02 percent NaN3, flow rate: 0.5 mL / min, pressure: 20 bar, detectors: refractive index and UV multi-wavelength).
  • the OligoUlvane extract preferably has the following characteristics (in percentages by weight):
  • HP-SEC Bipopulated from 17,000 to 25,000 Da (majority) and from 66,000 to 80,000 Da.
  • the invention also relates to a method for producing an extract comprising at least one ulvan oligomer as defined above, comprising the following steps:
  • the invention also relates to a method for producing an extract according to the invention, comprising the following steps:
  • the algae used are Ulva lactuca.
  • step (i) takes place at a temperature of about 80 ° C.
  • “maceration” is meant a step of letting the algae or seaweed extract remain in a liquid that is not boiled. This step makes it possible to extract the soluble compounds from the algae.
  • step (ii) takes place at a temperature of about 80 ° C.
  • the pH of the solution at this stage is between 1 and 3, in particular the pH is 2.
  • the acidic pH of the solution can be obtained by adding HCl.
  • step (iii) NaOH is used as the strong base.
  • the clarification step may be carried out by a step or by a succession of sub-stages of spin-offs and filtrations.
  • the clarification step makes it possible to obtain a solution free of particles of more than 0.5 ⁇ m.
  • the sterilizing filtration step is a step well known to those skilled in the art.
  • the purification step can be carried out by a succession of sub-steps allowing the separation of the desired oligomer from the other compounds of the solution.
  • This step may in particular comprise a separation step by chromatography, centrifugation, extraction and / or crystallization.
  • the products obtained by the processes according to the invention are kept dry and cold, more preferably between 0 and 10 ° C. and preferably at about 4 ° C.
  • the invention also relates to an ulvan oligomer that can be obtained by the process for producing an extract comprising at least one ulvan oligomer according to the invention.
  • the invention further relates to an extract comprising at least one ulvan oligomer obtainable by the process for producing an extract comprising at least one ulvan oligomer according to the invention.
  • the invention also relates to a particularly cosmetic composition containing at least one ulvan oligomer as defined above and / or an extract according to the invention.
  • the invention also relates to a particularly cosmetic composition that can be obtained by the process for producing an extract comprising at least one ulvan oligomer according to the invention.
  • the invention also relates to a non-therapeutic cosmetic use of a composition according to the invention for softening and / or reducing the tightness of the skin.
  • the invention thus relates to the non-therapeutic cosmetic use of at least one ulvan oligomer as defined above or an extract as defined above or a cosmetic composition as defined above to soften and / or reduce the tightness of the skin.
  • skin is meant human skin and / or human scalp.
  • skin is meant in particular the skin of the body, especially the legs, arms, hands, neck and the skin of the face.
  • softening it is intended herein to increase the suppleness, flexibility or elasticity of the skin, and / or to increase the softness of the skin, and / or to limit the appearance of wrinkles and fine lines.
  • the composition used according to the invention or the extract used according to the invention comprises between 0.01 and 20% ulvan oligomer (s) as defined above more particularly between 0. , 5 and 10%, more particularly between 1 and 7% by weight relative to the dry weight of the composition.
  • the composition according to the invention or the extract according to the invention can be used in a subject having a sensitive skin and in particular a dry and / or aged skin. According to one embodiment, the composition according to the invention or the extract according to the invention can be used in a subject having a dry scalp.
  • composition used according to the invention or the extract used according to the invention is intended for topical application.
  • compositions used according to the invention preferentially contain a physiologically acceptable medium, that is to say compatible with the skin.
  • This physiologically acceptable medium may more particularly consist of water and optionally of a physiologically acceptable organic solvent chosen, for example, from lower alcohols containing from 1 to 8 carbon atoms and in particular from 1 to 6 carbon atoms, such as ethanol, isopropanol, propanol, butanol; polyethylene glycols having from 6 to 80 ethylene oxide units and polyols such as propylene glycol, isoprene glycol and butylene glycol.
  • Said composition may especially be in the form of a cream or lotion, for example of daily application, a liquid or solid soap, a shower gel, a mask treatment, a patch, a shampoo, a conditioner, a lotion or a gel.
  • composition according to the invention or the extract according to the invention can also be used to moisturize the skin.
  • compositions according to the invention are those generally used in the fields under consideration.
  • these compositions are prepared according to the usual methods.
  • the composition is used according to the invention as active agent at an effective amount, that is to say at a quantity allowing it to have the desired effect.
  • the composition used comprises between 2 and 15% by weight relative to the total weight of the composition, extract comprising at least one ulvan oligomer as defined above.
  • composition of the invention is preferably an aqueous composition.
  • composition may furthermore comprise at least one adjuvant, especially adjuvants conventionally employed in the cosmetics field, and especially chosen from oils; waxes, pigments, fillers, dyes, surfactants, emulsifiers; cosmetic active ingredients, UV filters, polymers, thickeners, film-forming polymers, preservatives, perfumes, bactericides, odor absorbers, antioxidants.
  • adjuvants especially adjuvants conventionally employed in the cosmetics field, and especially chosen from oils; waxes, pigments, fillers, dyes, surfactants, emulsifiers; cosmetic active ingredients, UV filters, polymers, thickeners, film-forming polymers, preservatives, perfumes, bactericides, odor absorbers, antioxidants.
  • compositions are those conventionally used in the field under consideration, and for example from 0.01 to 20% of the total weight of the composition.
  • the invention also relates to a cosmetic process for softening and / or reducing skin tightness comprising a topical application step, an effective amount of a composition according to the invention or an extract according to the invention. the invention.
  • 164 g of Ulva lactuca seaweed powder is used to make a 5% aqueous solution.
  • the 5% aqueous solution is heated at 80 ° C. for 2 hours with constant stirring.
  • the filtrate is clarified until sterilization (at 0.2 microns) and then atomized.
  • HP-SEC Bipopulated from 17,000 to 25,000 Da (majority) and from 66,000 to 80,000 Da.
  • the DMA (Dynamic Mechanical Analysis) apparatus sold under the reference ElectroForce® 3100 by the company Bose was used.
  • This technique makes it possible to study the viscoelastic properties of the stratum corneum.
  • the material is sinusoidally stressed and its deformation is measured.
  • the conservation module (E ') of the stratum corneum can thus be determined.
  • the conservation module makes it possible to characterize the stratum corneum mechanically. This size is directly related to the elastic properties of the stratum corneum.
  • the impact of several sulphated saccharides on this conservation module has been studied, notably the OligoUlvane extract of Example 1 and two other compositions which have been prepared according to the protocol described in patent application FR2982152 from Ulva Rotundata. and Ulva Armoricana.
  • the surface of the Stratum Corneum sample to be tested is 2 cm 2 (1 cm c 2 cm).
  • the samples were preconditioned at 75% relative humidity for a minimum of 12 hours, and the measurement was also carried out at 75% relative humidity.
  • Solutions of raw materials at 5% by mass (dry extract) were prepared in water and 10 mI / cm 2 were deposited on each stratum corneum sample. The solution was spread on the stratum corneum so as to cover the entire surface.
  • the dynamic amplitude of stress was set at 40 ⁇ m, which corresponds to a deformation in the elastic domain of the stratum corneum (0.2% deformation). Each sample was solicited at the frequency of 10 Hz, according to the greatest length. Stratum corneum samples from several donors were used to verify that the results are consistent and repeatable.
  • the OligoUlvane extract of the invention has the strongest softening effect, close to the positive reference (glycerol).
  • Example 3 Cosmetic composition (% by weight)
  • This composition can be applied daily on the body.

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Abstract

The present invention relates to a particular extract of sulfated oligosaccharides, comprising an ulvan oligomer, to a method for the production thereof, to compositions comprising the extract, and to a cosmetic skin treatment method using said extract.

Description

Oligosaccharides sulfatés et leurs utilisations cosmétiques  Sulphated oligosaccharides and their cosmetic uses
La présente invention concerne un extrait particulier d’oligosaccharides sulfatés, son procédé de production et un procédé de traitement cosmétique de la peau utilisant cet extrait. The present invention relates to a particular extract of sulfated oligosaccharides, its production method and a method of cosmetic treatment of the skin using this extract.
La peau est un tissu dont les cellules sont jointives, et solidaires les unes des autres. Le tissu cutané forme un revêtement externe comprenant des glandes sébacées ou sudoripares, et les follicules pileux. Les tissus cutanés comprennent la peau et le cuir chevelu, qui sont des épithéliums à renouvellement continuel. Le renouvellement, ou desquamation, est un processus coordonné et finement régulé aboutissant à l'élimination des cellules superficielles, de façon insensible et non visible. The skin is a tissue whose cells are contiguous and integral with each other. The cutaneous tissue forms an outer covering comprising sebaceous or sweat glands, and hair follicles. The cutaneous tissues include the skin and the scalp, which are epitheliums with continual renewal. Renewal, or desquamation, is a coordinated and finely regulated process resulting in the elimination of surface cells, insensitively and nonvisibly.
Le tissu cutané est constitué de deux compartiments à savoir un compartiment superficiel, l’épiderme, et un compartiment profond, le derme.  The cutaneous tissue consists of two compartments namely a superficial compartment, the epidermis, and a deep compartment, the dermis.
L'épiderme est conventionnellement divisé en une couche basale de kératinocytes constituant la couche germinative de l'épiderme, une couche dite épineuse constituée de plusieurs couches de cellules polyhédriques disposées sur les couches germinatives, une à trois couches dites granuleuses constituées de cellules aplaties contenant des inclusions cytoplasmiques distinctes, les grains de kératohyaline et enfin, un ensemble de couches supérieures appelées couches cornées (ou stratum corneum), constituées de kératinocytes au stade terminal de leur différenciation appelés cornéocytes.  The epidermis is conventionally divided into a basal layer of keratinocytes constituting the germinal layer of the epidermis, a so-called spinous layer consisting of several layers of polyhedral cells arranged on the germinal layers, one to three so-called granular layers consisting of flattened cells containing distinct cytoplasmic inclusions, keratohyaline grains and finally, a set of upper layers called horny layers (or stratum corneum), consisting of keratinocytes at the terminal stage of their differentiation called corneocytes.
Les cornéocytes sont des cellules anucléées principalement constituées d'une matière fibreuse contenant des cytokératines, entourée d'une enveloppe cornée. Il y a en permanence production de nouveaux kératinocytes pour compenser la perte en continu de cellules épidermiques au niveau de la couche cornée selon un mécanisme dénommé desquamation.  Corneocytes are anucleate cells consisting primarily of a fibrous material containing cytokeratins, surrounded by a horny envelope. There is constantly production of new keratinocytes to compensate for the continuous loss of epidermal cells in the stratum corneum by a mechanism called desquamation.
Les troubles du stratum corneum peuvent aboutir à une fragilité, voire un défaut des propriétés barrières de l’épiderme, à une déshydratation chronique du stratum corneum, une perte d'élasticité mécanique, un inconfort cutané et à des tiraillements.  Stratum corneum disorders can lead to fragility, even a lack of barrier properties of the epidermis, chronic dehydration of the stratum corneum, loss of mechanical elasticity, cutaneous discomfort and tightness.
À titre d'exemple de facteurs favorisant l’altération de la qualité de surface de la peau, on peut mentionner le stress, la période hivernale, un excès de sébum, un défaut d'hydratation. Ces désordres apparaissent aussi dans le cas des peaux sèches et/ou de sujets âgés.  As an example of factors promoting the deterioration of the surface quality of the skin, mention may be made of stress, the winter period, an excess of sebum, a lack of hydration. These disorders also occur in the case of dry skin and / or elderly subjects.
Ainsi une altération de la barrière cutanée peut se produire en présence d'agressions externes comme avec des détergents, des acides, des bases, des oxydants, des réducteurs, des solvants concentrés, des gaz ou des fumées nocives, et/ou suite à des sollicitations mécaniques (frottements, chocs, abrasion, arrachement de la surface, projection de poussières, de particules), et/ou des déséquilibres thermiques ou climatiques (froid, sécheresse), ou suite à un stress psychologique. Thus an alteration of the skin barrier can occur in the presence of external aggressions as with detergents, acids, bases, oxidants, reducing agents, concentrated solvents, gases or harmful fumes, and / or following mechanical stress (friction, shock, abrasion, tearing of the surface, projection of dust, particles), and / or thermal or climatic imbalances (cold, dryness), or following psychological stress.
La demande de brevet FR2982152 décrit certains polysaccharides pour améliorer la fonction barrière de la peau, notamment favoriser l’hydratation. L’application de ces polysaccharides produit une sensation de confort (absence de tiraillement de la peau).  Patent application FR2982152 describes certain polysaccharides to improve the skin's barrier function, in particular to promote hydration. The application of these polysaccharides produces a sensation of comfort (absence of tightness of the skin).
Cependant il y a toujours un besoin de nouveaux actifs permettant d’assouplir et/ou diminuer le tiraillement de la peau et éventuellement permettant d’améliorer l’état d'hydratation des tissus cutanés, en particulier des peaux sèches ou âgées, en évitant les tiraillements et les sensations d'inconfort.  However, there is still a need for new active agents to soften and / or reduce the tightness of the skin and possibly to improve the hydration state of the skin tissues, particularly dry or aged skin, avoiding the tugging and feelings of discomfort.
De manière inattendue, la demanderesse a découvert que de meilleurs résultats peuvent être obtenus en utilisant un extrait comprenant des oligosaccharides sulfatés particuliers qui favorisent la souplesse des tissus cutanés, en particulier du stratum corneum et génèrent ainsi une sensation de confort. Ces oligosaccharides peuvent notamment être obtenus en hydrolysant spécifiquement les ulvanes décrits dans la demande de brevet FR2982152.  Unexpectedly, the Applicant has discovered that better results can be obtained by using an extract comprising particular sulphated oligosaccharides which promote the softness of the cutaneous tissues, in particular the stratum corneum and thus generate a feeling of comfort. These oligosaccharides may in particular be obtained by specifically hydrolysing the ulvans described in the patent application FR2982152.
La présente invention concerne un extrait comprenant au moins un oligomère d’ulvane ayant un poids moléculaire entre 5000 Da et 90 000 Da, et préférence entre 15000 Da et 92 000 Da et plus particulièrement entre 16 000 Da et 85 000 Da. The present invention relates to an extract comprising at least one ulvan oligomer having a molecular weight between 5000 Da and 90 000 Da, and preferably between 15000 Da and 92 000 Da and more particularly between 16 000 Da and 85 000 Da.
En particulier l’extrait comprenant au moins un oligomère d’ulvane selon l’invention présente notamment deux populations de poids moléculaires différents, de 15000 à 30000 Da en particulier de 17000 à 25000 Da pour la première population appelée par la suite population A, et de 55000 à 90000 Da en particulier de 66000 à 80000 Da pour la seconde population appelée par la suite population B. Selon une forme particulière de l’invention le rapport massique entre la population A, comprenant des oligomères de poids moléculaire plus faible, et la population B, comprenant des oligomères de poids moléculaire plus élevé, est supérieur à 1. In particular, the extract comprising at least one ulvan oligomer according to the invention has in particular two populations of different molecular weights, from 15,000 to 30,000 Da, in particular from 17,000 to 25,000 Da for the first population, hereinafter referred to as population A, and from 55000 to 90000 Da, in particular from 66000 to 80000 Da for the second population, hereinafter referred to as population B. According to one particular form of the invention, the mass ratio between the population A, comprising oligomers of lower molecular weight, and the population B, comprising oligomers of higher molecular weight, is greater than 1.
L’invention a également pour objet une composition notamment cosmétique contenant au moins un oligomère d’ulvane tel que défini ci-dessous et/ou un extrait selon l’invention. The invention also relates to a particularly cosmetic composition containing at least one ulvan oligomer as defined below and / or an extract according to the invention.
L’invention a aussi pour objet un procédé de traitement cosmétique de la peau mettant en oeuvre au moins un oligomère d’ulvane tel que défini ci-dessous ou au moins un extrait selon l’invention ou une composition selon l’invention, pour assouplir et/ou diminuer le tiraillement de la peau. The subject of the invention is also a process for cosmetic treatment of the skin using at least one ulvan oligomer as defined below or at least an extract according to the invention or a composition according to the invention for softening and / or reducing the tightness of the skin.
Oliqomère d’ulvane Oliqomer of ulvane
Par « oligomères » on entend des oligosaccharides sulfatés comprenant de préférence entre 25 et 500 oses et en particulier entre 90 et 150 oses. Oligomers are understood to mean sulphated oligosaccharides preferably comprising between 25 and 500 monosaccharides and in particular between 90 and 150 monosaccharides.
Les ulvanes sont des polysaccharides anioniques sulfatés contenant du rhamnose obtenus à partir d'algues vertes appartenant à l'ordre des ulvales. Les ulvanes sont des polysaccharides anioniques sulfatés solubles dans l'eau qui sont localisés dans la paroi cellulaire. Les ulvanes sont notamment extraits des ulves ou des entéromorphes. Ces algues de couleur verte font partie du phylum des chlorophytes et de l'ordre des ulvales caractérisées par un thalle en tube (entéromorphe) ou en double couche cellulaire (ulve). Ulvans are sulphated anionic polysaccharides containing rhamnose obtained from green algae belonging to the order of the ulvals. Ulvans are water-soluble sulfated anionic polysaccharides that are localized in the cell wall. Ulvans are particularly extracted from ulvae or enteromorphs. These green algae are part of the phylum of chlorophytes and of the order of the ulvals characterized by a thallus in tube (enteromorphic) or double cell layer (ulve).
Les ulvanes représentent de 8 à 29 % du poids sec des algues. Ils sont principalement constitués de rhamnose, d'acide glucuronique, de glucose, de galactose et de xylose et comprennent aussi des groupements sulfatés. Ils peuvent également comprendre des quantités variables d'acide galacturonique, d'acide iduronique et de mannose.  Ulvans account for 8 to 29% of the dry weight of algae. They consist mainly of rhamnose, glucuronic acid, glucose, galactose and xylose and also include sulphated groups. They may also include varying amounts of galacturonic acid, iduronic acid and mannose.
Le rhamnose est généralement sulfaté en position 3. Le xylose peut également être partiellement sulfaté. La plupart des sucres constitutifs sont distribués selon des séquences répétitives. Les deux séquences majeures sont des séquences disaccharidiques, l'une dénommée acide ulvanobiuronique à 3 sulfates dite de type A (A3s) comprenant du rhamnose 3-sulfate lié à de l'acide glucuronique par une liaison de type 1 4, l'autre dénommée acide ulvanobiuronique à 3 sulfates dite de type B (B3s) comprenant du rhamnose 3-sulfate lié à de l'acide iduronique par une liaison de type 1 4.  Rhamnose is generally sulphated at position 3. Xylose may also be partially sulphated. Most of the constituent sugars are distributed according to repetitive sequences. The two major sequences are disaccharide sequences, one called ulvanobiuronic acid with 3 type A sulfates (A3s) comprising rhamnose 3-sulfate linked to glucuronic acid by a type 1 link 4, the other denominated 3-type ulvanobiuronic acid type B (B3s) comprising rhamnose 3-sulfate linked to iduronic acid by a type 1 linkage 4.
La proportion relative des sucres est variable selon le lieu de récolte des ulves, l'espèce et le moment de récolte dans l'année.  The relative proportion of sugars varies according to the place of harvest of the ulva, the species and the time of harvest in the year.
De manière préférée, les oligomères d’ulvanes de l’invention comprennent du rhamnose, de l’acide glucuronique, de l’acide iduronique, du xylose, du galactose et du glucose. De préférence, l’extrait comprenant au moins un oligomère d’ulvane selon l’invention, a un taux de sulfates greffés sur le ou les oligomères d’ulvanes compris entre 4 et 15%, plus particulièrement entre 6% et 12%, et de préférence entre 7 et 10%, en particulier 7,5%, en poids par rapport au poids sec de l’extrait. Preferably, the ulvan oligomers of the invention comprise rhamnose, glucuronic acid, iduronic acid, xylose, galactose and glucose. Preferably, the extract comprising at least one ulvan oligomer according to the invention has a content of sulphates grafted onto the oligomer (s) of ulvans of between 4 and 15%, more particularly between 6% and 12%, and preferably between 7 and 10%, in particular 7.5%, by weight relative to the dry weight of the extract.
L’oligomère d’ulvane selon l’invention provient préférablement d’Ulva lactuca. The ulvan oligomer according to the invention is preferably from Ulva lactuca.
L’extrait comprenant au moins un oligomère d’ulvane selon l’invention est de préférence préparé à partir de l’algue verte Ulva lactuca. The extract comprising at least one ulvan oligomer according to the invention is preferably prepared from the green alga Ulva lactuca.
L’extrait comprenant au moins un oligomère d’ulvane selon l’invention provient donc préférablement d’Ulva lactuca.  The extract comprising at least one ulvan oligomer according to the invention therefore preferably comes from Ulva lactuca.
La présente invention concerne également un extrait comprenant au moins un oligomère d’ulvane selon l’invention. The present invention also relates to an extract comprising at least one ulvan oligomer according to the invention.
En particulier l’extrait selon l’invention comprend au moins un oligomère d’ulvane ayant un poids moléculaire moyen entre 5000 Da et 90 000 Da, de préférence entre 15 000 Da et 92 000 Da et plus particulièrement entre 16 000 Da et 85 000 Da.  In particular, the extract according to the invention comprises at least one ulvan oligomer having an average molecular weight between 5000 Da and 90 000 Da, preferably between 15 000 Da and 92 000 Da and more particularly between 16 000 Da and 85 000 da.
En particulier l’extrait selon l’invention comprend au moins un oligomère d’ulvane (a) de poids moléculaire compris entre 15 000 et 30 000 Da en particulier compris entre 17 000 à 25 000 Da, et au moins un oligomère d’ulvane (b) de poids moléculaire compris entre 55 000 et 90 000 Da en particulier compris entre 66 000 à 80 000 Da.  In particular, the extract according to the invention comprises at least one oligomer of ulvan (a) with a molecular weight of between 15,000 and 30,000 Da, in particular between 17,000 and 25,000 Da, and at least one ulvan oligomer. (b) of molecular weight between 55,000 and 90,000 Da in particular between 66,000 to 80,000 Da.
Selon une forme particulière de l’invention, dans l’extrait selon l’invention, la masse totale d’oligomères d’ulvane de type (a) est supérieure à la masse totale d’oligomères d’ulvane de type (b).  According to one particular form of the invention, in the extract according to the invention, the total mass of ulvan oligomers of type (a) is greater than the total mass of ulvan oligomers of type (b).
De préférence l’extrait selon l’invention ne comprend pas de polysaccharides sulfatés ayant un poids moléculaire supérieur à 250 000 Da et plus particulièrement supérieur à 150 000 Da et préférentiellement ne comprend pas de polysaccharides sulfatés ayant un poids moléculaire supérieur à 100 000 Da. Preferably, the extract according to the invention does not comprise sulphated polysaccharides having a molecular weight greater than 250,000 Da and more particularly greater than 150,000 Da and preferably does not comprise sulphated polysaccharides having a molecular weight greater than 100,000 Da.
De préférence, dans l’extrait selon l’invention, le taux de sulfatation moyen du ou des oligomères d’ulvane est compris entre 4 et 15%, plus particulièrement entre 6% et 12%, et de préférence entre 7 et 10%, en poids par rapport au poids sec de l’extrait de l’invention. Selon une forme particulière de l’invention, dans l’extrait selon l’invention, le taux de sulfatation moyen du ou des oligomères d’ulvane est de 7,5%.  Preferably, in the extract according to the invention, the average sulfation rate of the ulvan oligomer (s) is between 4 and 15%, more particularly between 6% and 12%, and preferably between 7 and 10%, by weight relative to the dry weight of the extract of the invention. According to one particular form of the invention, in the extract according to the invention, the average sulfation rate of the ulvan oligomer (s) is 7.5%.
Selon une forme particulière de l’invention, l’extrait comprend des protéines. Lorsque des protéines sont présentes, elles constituent de préférence de 0,01 à 15%, plus particulièrement de 0,1% à 10%, plus préférentiellement de 1% à 8% et notamment de 2% à 5% tel que 2,95% en poids par rapport au poids sec de l’extrait. Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait comprennent essentiellement du rhamnose, puis par masses présentes décroissantes, de l’acide glucuronique dans une quantité du même ordre que l’acide iduronique, puis dans des quantités moindres, du xylose, du galactose et du glucose. According to a particular form of the invention, the extract comprises proteins. When proteins are present, they preferably constitute from 0.01 to 15%, more particularly from 0.1% to 10%, more preferably from 1% to 8%, and especially from 2% to 5%, such as 2.95%. % by weight relative to the dry weight of the extract. According to one particular form of the invention, the oligomers of ulvans contained in the extract essentially comprise rhamnose and then, by decreasing masses, glucuronic acid in a quantity of the same order as iduronic acid, then in smaller amounts, xylose, galactose and glucose.
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait comprennent de 20 à 30%, plus particulièrement 24,4%, en poids de rhamnose par rapport au poids sec de l’extrait.  According to one particular form of the invention, the oligomers of ulvans contained in the extract comprise from 20 to 30%, more particularly 24.4%, by weight of rhamnose relative to the dry weight of the extract.
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait comprennent 5 à 15%, plus préférentiellement 8 à 12% et notamment 10,6%en poids d’acide glucuronique par rapport au poids sec de l’extrait.  According to one particular form of the invention, the oligomers of ulvans contained in the extract comprise 5 to 15%, more preferably 8 to 12% and in particular 10.6% by weight of glucuronic acid relative to the dry weight of the 'extract.
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait comprennent 5 à 15%, plus préférentiellement 10 à 15% et notamment de 12,1% en poids d’acide iduronique par rapport au poids sec de l’extrait.  According to one particular form of the invention, the oligomers of ulvans contained in the extract comprise 5 to 15%, more preferably 10 to 15% and especially 12.1% by weight of iduronic acid relative to the dry weight of the extract.
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait comprennent 1 à 10% en poids de chacun des sucres parmi le xylose, le galactose et le glucose par rapport au poids sec de l’extrait.  According to one particular form of the invention, the oligomers of ulvans contained in the extract comprise 1 to 10% by weight of each of the sugars among xylose, galactose and glucose relative to the dry weight of the extract.
Selon une forme particulière de l'invention, les oligomères d'ulvanes contenus dans l'extrait comprennent 1 à 10%, plus particulièrement 3,5% en poids de xylose par rapport au poids sec de l'extrait.  According to one particular form of the invention, the oligomers of ulvans contained in the extract comprise 1 to 10%, more particularly 3.5% by weight of xylose relative to the dry weight of the extract.
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait comprennent 1 à 10%, plus particulièrement 2,4% en poids de galactose par rapport au poids sec de l’extrait.  According to one particular form of the invention, the oligomers of ulvans contained in the extract comprise 1 to 10%, more particularly 2.4% by weight of galactose relative to the dry weight of the extract.
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait comprennent 1 à 10%, plus particulièrement 5,7% en poids de glucose par rapport au poids sec de l’extrait.  According to one particular form of the invention, the oligomers of ulvans contained in the extract comprise 1 to 10%, more particularly 5.7% by weight of glucose relative to the dry weight of the extract.
Selon une forme plus particulière de l'invention, les oligomères d'ulvanes convenus dans l'extrait comprennent 20 à 30%, plus particulièrement 24,4% en poids de rhamnose par rapport au poids sec de l’extrait, 8 à 12%, plus particulièrement 10,6 en poids d’acide glucuronique par rapport au poids sec de l’extrait, 10 à 15%, plus particulièrement 12,1% en poids d’acide iduronique par rapport au poids sec de l’extrait, 1 à 10%, plus particulièrement 3,5% en poids de xylose par rapport au poids sec de l'extrait, 1 à 10%, plus particulièrement 2,4% en poids de galactose par rapport au poids sec de l'extrait et 1 à 10%, plus particulièrement 5,7% en poids de glucose par rapport au poids sec de l'extrait. L’extrait selon l’invention peut comprendre en outre des matières minérales telles que définies par la suite. According to a more particular form of the invention, the oligomers of ulvans agreed in the extract comprise 20 to 30%, more particularly 24.4% by weight of rhamnose relative to the dry weight of the extract, 8 to 12% , more particularly 10.6% by weight of glucuronic acid relative to the dry weight of the extract, 10 to 15%, more particularly 12.1% by weight of iduronic acid relative to the dry weight of the extract, 1 at 10%, more particularly 3.5% by weight of xylose relative to the dry weight of the extract, 1 to 10%, more particularly 2.4% by weight of galactose relative to the dry weight of the extract and 1 at 10%, more particularly 5.7% by weight of glucose relative to the dry weight of the extract. The extract according to the invention may further comprise mineral substances as defined below.
De préférence, l’extrait selon l’invention comprend en outre entre 0 et 50% de matière minérale, plus particulièrement entre 5 et 40%, plus particulièrement entre 25 et 35% en poids, tel que 30% ou 30,1% en poids par rapport au poids sec de l’extrait.  Preferably, the extract according to the invention also comprises between 0 and 50% of mineral matter, more particularly between 5 and 40%, more particularly between 25 and 35% by weight, such as 30% or 30.1% by weight. weight relative to the dry weight of the extract.
Par « matière minérale » on entend la matière restante après séchage de l’extrait selon l’invention et calcination du produit du séchage. Par exemple le séchage peut être réalisé dans une étuve ventilée pendant 24h à 103°C. La calcination peut être réalisée pendant 12h à 550°C.  By "mineral material" is meant the material remaining after drying of the extract according to the invention and calcination of the drying product. For example, the drying can be carried out in a ventilated oven for 24 hours at 103 ° C. The calcination can be carried out for 12 hours at 550 ° C.
Pour l'obtention d'ulvanes par extraction à partir de l'ulve, on peut se reporter aux procédés d'extraction décrits dans Carbohydrate Research 274 (1995) 251 -261 ou dans Hydrobiologia 326/327;473-480,1996.  To obtain ulvans by extraction from ulva, reference can be made to the extraction methods described in Carbohydrate Research 274 (1995) 251-261 or in Hydrobiologia 326/327, 473-480, 1996.
Par exemple, l'extraction des ulvanes peut être réalisée à partir des algues séchées.  For example, the extraction of ulvans can be carried out from dried algae.
De préférence, l’extrait selon l’invention comprend entre 50 et 100% de matière organique plus particulièrement entre 60 et 95%, plus particulièrement entre 65 et 75% en poids, tel que 70% ou 66,9% en poids par rapport au poids sec de l’extrait.  Preferably, the extract according to the invention comprises between 50 and 100% of organic matter, more particularly between 60 and 95%, more particularly between 65 and 75% by weight, such as 70% or 66.9% by weight relative to to the dry weight of the extract.
De préférence, l’extrait selon l’invention comprend entre 20 et 80% d’oligomère(s) d’ulvane, plus particulièrement entre 25 et 60%, plus préférentiellement entre 30 et 50% en poids, tel que 40% en poids par rapport au poids sec de l’extrait. Preferably, the extract according to the invention comprises between 20 and 80% oligomer (s) of ulvan, more particularly between 25 and 60%, more preferably between 30 and 50% by weight, such as 40% by weight. relative to the dry weight of the extract.
Selon une forme particulière de l’invention, le taux de sulfate greffés sur les oligomères d’ulvanes de l’extrait est de 4 à 15%, plus particulièrement de 6% à 12%, et de préférence de 7 à 10%, tel que 7,5% en poids par rapport au poids sec de l’extrait. According to one particular form of the invention, the level of sulphate grafted on the ulvan oligomers of the extract is from 4 to 15%, more particularly from 6% to 12%, and preferably from 7 to 10%, such as than 7.5% by weight relative to the dry weight of the extract.
Selon une forme particulière de l’invention, le taux de sulfate libre de l’extrait est de 0 à 20%, plus particulièrement de 5% à 15%, et de préférence de 8 à 14%, tel que 1 1 ,8% en poids par rapport au poids sec de l’extrait de l’invention. According to one particular form of the invention, the level of free sulfate of the extract is from 0 to 20%, more particularly from 5% to 15%, and preferably from 8 to 14%, such as 1 1, 8%. by weight relative to the dry weight of the extract of the invention.
Selon une forme particulière de l’invention, le taux de sodium (Na) de l’extrait est de 10 à 15%, plus particulièrement de 1 1 ,38% en poids par rapport au poids sec de l’extrait. Selon une forme plus particulière de l'invention, l'extrait selon l’invention comprend entre 65 et 75%, plus particulièrement 66,90% en poids de matière organique par rapport au poids sec de l'extrait, 25 à 35%, plus particulièrement 30,1% en poids de matière minérale par rapport au poids sec de l'extrait, 10 à 15%, plus particulièrement 1 1 ,38% en poids de Na par rapport au poids sec de l'extrait, 2 à 5%, plus particulièrement 2,95%, en poids de protéines par rapport au poids sec de l'extrait, 30 à 50%, plus particulièrement 40%, en poids de sucres totaux (équivalent glucose) par rapport au poids sec de l'extrait, 7 à 14%, plus particulièrement 1 1 ,8%, en poids de sulfate libre par rapport au poids sec de l'extrait, 7 à 10%, plus particulièrement 7,5% en poids de sulfate greffés par rapport au poids sec de l'extrait. According to one particular form of the invention, the sodium (Na) content of the extract is 10 to 15%, more particularly 1 1, 38% by weight relative to the dry weight of the extract. According to a more particular form of the invention, the extract according to the invention comprises between 65 and 75%, more particularly 66.90% by weight of organic matter relative to the dry weight of the extract, 25 to 35%, more particularly 30.1% by weight of mineral matter relative to the dry weight of the extract, 10 to 15%, more particularly 1 1, 38% by weight of Na relative to the dry weight of the extract, 2 to 5 %, more particularly 2.95%, by weight of protein relative to the dry weight of the extract, 30 to 50%, more particularly 40%, by weight of total sugars (glucose equivalent) relative to the dry weight of the extract, 7 to 14%, more particularly 1 1, 8%, by weight of free sulfate relative to the dry weight of the extract, 7 to 10%, more particularly 7.5% by weight of grafted sulfate relative to the weight dry extract.
L’extrait selon l’invention peut être le nouvel extrait nommé par la demanderesse « OligoUlvane ». L’OIigoUlvane est produit à partir d’Ulva lactuca et contient des oligomères d’ulvanes. The extract according to the invention may be the new extract named by the Applicant "OligoUlvane". OIigoUlvane is produced from Ulva lactuca and contains oligomers of ulvans.
Selon une forme particulière de l’invention, les oligomères d’ulvanes représentent en équivalent glucose 20 à 80%, plus particulièrement entre 25 et 60%, plus préférentiellement entre 30 et 50% en poids, tel que 40% en poids par rapport au poids sec de l’extrait OligoUlvane.  According to one particular form of the invention, the oligomers of ulvans represent, in glucose equivalent, from 20 to 80%, more particularly from 25 to 60%, more preferably from 30 to 50% by weight, such as 40% by weight relative to dry weight of OligoUlvane extract.
Selon une forme particulière de l’invention, l’extrait sec de l’OIigoUlvane comprend de 0 à 50% de matière minérale, plus particulièrement de 5 à 40%, plus préférentiellement de 25 à 35% en poids, tel que 30% ou 30,1% en poids par rapport au poids sec de l’extrait OligoUlvane.  According to one particular form of the invention, the dry extract of OIigoUlvane comprises from 0 to 50% of mineral matter, more particularly from 5 to 40%, more preferably from 25 to 35% by weight, such as 30% or 30.1% by weight relative to the dry weight of OligoUlvane extract.
Selon une forme particulière, l’extrait sec de l’OIigoUlvane comprend entre 50 et 100% de matière organique plus particulièrement entre 60 et 95%, plus particulièrement entre 65 et 75% en poids, tel que 70% ou 66,9% en poids par rapport au poids sec de l’extrait OligoUlvane.  According to one particular form, the dry extract of OIigoUlvane comprises between 50 and 100% of organic matter, more particularly between 60 and 95%, more particularly between 65 and 75% by weight, such as 70% or 66.9% by weight. weight relative to the dry weight of OligoUlvane extract.
Dans l’OIigoUlvane, les oligomères d’ulvanes ont un poids moléculaire moyen entre 5000 Da et 90 000 Da, de préférence entre 15 000 Da et 92 000 Da et plus particulièrement entre 16 000 Da et 85 000 Da. In OligoUlvane, the oligomers of ulvans have an average molecular weight between 5000 Da and 90 000 Da, preferably between 15 000 Da and 92 000 Da and more particularly between 16 000 Da and 85 000 Da.
Selon une forme particulière de l’invention, les oligomères d’ulvanes compris dans l’extrait OligoUlvane tel que défini précédemment sont des oligomères de poids moléculaire allant de 15 000 à 30 000 Da, en particulier compris entre 17 000 à 25 000 Da, et des oligomères de poids moléculaire allant de 55 000 à 90 000 Da, en particulier compris entre 66 000 à 80 000 Da. Selon une forme particulière de l’invention, dans l’extrait OligoUlvane, la masse totale d’oligomères d’ulvanes de poids moléculaire allant de 15 000 à 30 000 Da est supérieure à la masse totale d’oligomères d’ulvanes de poids moléculaires allant de 55 000 à 90 000 Da. According to one particular form of the invention, the oligomers of ulvans included in the OligoUlvane extract as defined above are oligomers with a molecular weight ranging from 15,000 to 30,000 Da, in particular between 17,000 and 25,000 Da, and oligomers of molecular weight ranging from 55,000 to 90,000 Da, in particular from 66,000 to 80,000 Da. According to one particular form of the invention, in the OligoUlvane extract, the total mass of ulvan oligomers with a molecular weight ranging from 15,000 to 30,000 Da is greater than the total weight of molecular weight ulvan oligomers. ranging from 55,000 to 90,000 Da.
Selon une forme particulière de l’invention, le taux de sulfate greffés sur les oligomères d’ulvanes de l’extrait OligoUlvane est de 4 à 15%, plus particulièrement de 6% à 12%, et de préférence de 7 à 10%, tel que 7,5% en poids par rapport au poids sec de l’extrait OligoUlvane de l’invention. According to one particular form of the invention, the level of sulphate grafted on the ulvan oligomers of the OligoUlvane extract is from 4 to 15%, more particularly from 6% to 12%, and preferably from 7 to 10%, such as 7.5% by weight based on the dry weight of the OligoUlvane extract of the invention.
Selon une forme particulière de l’invention, le taux de sulfate libre de l’extrait OligoUlvane est de 0 à 20%, plus particulièrement de 5% à 15%, et de préférence de 8 à 14%, tel que 1 1 ,8% en poids par rapport au poids sec de l’extrait OligoUlvane de l’invention. According to one particular form of the invention, the level of free sulphate of the OligoUlvane extract is from 0 to 20%, more particularly from 5% to 15%, and preferably from 8 to 14%, such as 1 1, 8 % by weight relative to the dry weight of the OligoUlvane extract of the invention.
Selon une forme particulière de l’invention, le taux de sodium (Na) de l’extrait OligoUlvane est de 10 à 15%, plus particulièrement de 1 1 ,38% en poids par rapport au poids sec de l’extrait OligoUlvane de l’invention.  According to one particular form of the invention, the sodium (Na) content of the OligoUlvane extract is from 10 to 15%, more particularly from 1 to 38% by weight relative to the dry weight of the OligoUlvane extract. 'invention.
Selon une forme particulière de l’invention, l’extrait OligoUlvane comprend des protéines. Lorsque des protéines sont présentes, elles constituent de préférence de 0,01 à 15%, plus particulièrement de 0,1% à 10%, plus préférentiellement de 1 % à 8% et notamment de 2% à 5% tel que 2,95% en poids par rapport au poids sec de l’extrait OligoUlvane de l’invention. According to one particular form of the invention, the OligoUlvane extract comprises proteins. When proteins are present, they preferably constitute from 0.01 to 15%, more particularly from 0.1% to 10%, more preferably from 1% to 8%, and especially from 2% to 5%, such as 2.95%. % by weight relative to the dry weight of the OligoUlvane extract of the invention.
Selon une forme plus particulière de l'invention, l'extrait OligoUlvane comprend entre 65 et 75%, plus particulièrement 66,90% en poids de matière organique par rapport au poids sec de l'extrait OligoUlvane de l'invention, 25 à 35%, plus particulièrement 30,1% en poids de matière minérale par rapport au poids sec de l'extrait OligoUlvane de l'invention, 10 à 15%, plus particulièrement 1 1 ,38% en poids de Na par rapport au poids sec de l'extrait OligoUlvane de l'invention, 2 à 5%, plus particulièrement 2,95%, en poids de protéines par rapport au poids sec de l'extrait OligoUlvane de l'invention, 30 à 50%, plus particulièrement 40%, en poids de sucres totaux (équivalent glucose) par rapport au poids sec de l'extrait OligoUlvane de l'invention, 7 à 14%, plus particulièrement 1 1 ,8%, en poids de sulfate libre par rapport au poids sec de l'extrait OligoUlvane de l'invention, 7 à 10%, plus particulièrement 7,5% en poids de sulfate greffés par rapport au poids sec de l'extrait OligoUlvane de l'invention. Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait OligoUlvane comprennent du rhamnose, de l’acide glucuronique, de l’acide iduronique, du xylose, du galactose et du glucose. According to a more particular form of the invention, the OligoUlvane extract comprises between 65 and 75%, more particularly 66.90% by weight of organic matter relative to the dry weight of the OligoUlvane extract of the invention, 25 to 35% by weight. %, more particularly 30.1% by weight of mineral matter relative to the dry weight of the OligoUlvane extract of the invention, 10 to 15%, more particularly 1 1, 38% by weight of Na relative to the dry weight of the OligoUlvane extract of the invention, 2 to 5%, more particularly 2.95%, by weight of proteins relative to the dry weight of the OligoUlvane extract of the invention, 30 to 50%, more particularly 40%, by weight of total sugars (glucose equivalent) relative to the dry weight of the OligoUlvane extract of the invention, 7 to 14%, more particularly 1 1, 8%, by weight of free sulfate relative to the dry weight of the OligoUlvane extract of the invention, 7 to 10%, more particularly 7.5% by weight of grafted sulfate relative to the dry weight of the e OligoUlvane extract of the invention. According to one particular form of the invention, the oligomers of ulvans contained in the OligoUlvane extract comprise rhamnose, glucuronic acid, iduronic acid, xylose, galactose and glucose.
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait OligoUlvane comprennent essentiellement du rhamnose, puis par masses présentes décroissantes, de l’acide glucuronique dans une quantité du même ordre que l’acide iduronique, puis dans des quantités moindres, du xylose, du galactose et du glucose. According to one particular form of the invention, the oligomers of ulvans contained in the OligoUlvane extract essentially comprise rhamnose, then, in descending masses, glucuronic acid in a quantity of the same order as iduronic acid, then in smaller amounts, xylose, galactose and glucose.
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait OligoUlvane comprennent de 20 à 30%, plus particulièrement 24,4% en poids de rhamnose par rapport au poids sec de l’extrait OligoUlvane de l’invention.  According to one particular form of the invention, the oligomers of ulvans contained in the OligoUlvane extract comprise from 20 to 30%, more particularly 24.4% by weight of rhamnose relative to the dry weight of the OligoUlvane extract of the OligoUlvane extract. invention.
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait OligoUlvane comprennent 5 à 15%, plus préférentiellement 8 à 12% et notamment 10,6% en poids d’acide glucuronique par rapport au poids sec de l’extrait OligoUlvane de l’invention.  According to one particular form of the invention, the oligomers of ulvans contained in the OligoUlvane extract comprise 5 to 15%, more preferably 8 to 12% and in particular 10.6% by weight of glucuronic acid relative to the dry weight of the OligoUlvane extract of the invention.
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait OligoUlvane comprennent 5 à 15%, plus préférentiellement 10 à 15% et notamment 12,1% en poids d’acide iduronique par rapport au poids sec de l’extrait OligoUlvane de l’invention.  According to one particular form of the invention, the oligomers of ulvans contained in the OligoUlvane extract comprise 5 to 15%, more preferably 10 to 15% and in particular 12.1% by weight of iduronic acid relative to the dry weight of the OligoUlvane extract of the invention.
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait OligoUlvane comprennent 1 à 10% en poids de chacun des sucres parmi le xylose, le galactose et le glucose par rapport au poids sec de l’extrait OligoUlvane de l’invention.  According to one particular form of the invention, the oligomers of ulvans contained in the OligoUlvane extract comprise 1 to 10% by weight of each of the sugars among xylose, galactose and glucose relative to the dry weight of the OligoUlvane extract. of the invention.
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait OligoUlvane comprennent 1 à 10%, plus particulièrement 3,5% en poids de xylose par rapport au poids sec de l’extrait OligoUlvane de l'invention.  According to one particular form of the invention, the oligomers of ulvans contained in the OligoUlvane extract comprise 1 to 10%, more particularly 3.5% by weight of xylose relative to the dry weight of the OligoUlvane extract of the invention. .
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait OligoUlvane comprennent 1 à 10%, plus particulièrement 2,4% en poids de galactose par rapport au poids sec de l’extrait Oligoulvane de l'invention.  According to one particular form of the invention, the oligomers of ulvans contained in the OligoUlvane extract comprise 1 to 10%, more particularly 2.4% by weight of galactose relative to the dry weight of the Oligoulvane extract of the invention. .
Selon une forme particulière de l’invention, les oligomères d’ulvanes contenus dans l’extrait OligoUlvane comprennent 1 à 10%, plus particulièrement 5,7% en poids de glucose par rapport au poids sec de l’extrait OligoUlvane de l'invention. Selon une forme plus particulière de l'invention, les oligomères d'ulvanes convenus dans l'extrait OligoUlvane comprennent 20 à 30%, plus particulièrement 24,4% en poids de rhamnose par rapport au poids sec de l’extrait OligoUlvane de l'invention, 8 à 12%, plus particulièrement 10,6 en poids d’acide glucuronique par rapport au poids sec de l’extrait OligoUlvane de l'invention, 10 à 15%, plus particulièrement 12,1% en poids d’acide iduronique par rapport au poids sec de l’extrait OligoUlvane de l'invention, 1 à 10%, plus particulièrement 3,5% en poids de xylose par rapport au poids sec de l'extrait OligoUlvane de l'invention, 1 à 10%, plus particulièrement 2,4% en poids de galactose par rapport au poids sec de l'extrait OligoUlvane de l'invention et 1 à 10%, plus particulièrement 5,7% en poids de glucose par rapport au poids sec de l'extrait OligoUlvane de l'invention. According to one particular form of the invention, the oligomers of ulvans contained in the OligoUlvane extract comprise 1 to 10%, more particularly 5.7% by weight of glucose relative to the dry weight of the OligoUlvane extract of the invention. . According to a more particular form of the invention, the oligomers of ulvans agreed in the OligoUlvane extract comprise 20 to 30%, more particularly 24.4% by weight of rhamnose relative to the dry weight of the OligoUlvane extract of the OligoUlvane extract. 8 to 12%, more particularly 10.6% by weight of glucuronic acid relative to the dry weight of the OligoUlvane extract of the invention, 10 to 15%, more particularly 12.1% by weight of iduronic acid. relative to the dry weight of the OligoUlvane extract of the invention, 1 to 10%, more particularly 3.5% by weight of xylose relative to the dry weight of the OligoUlvane extract of the invention, 1 to 10%, more particularly 2.4% by weight of galactose with respect to the dry weight of the OligoUlvane extract of the invention and 1 to 10%, more particularly 5.7% by weight of glucose relative to the dry weight of the OligoUlvane extract of the invention.
Les teneurs en matière sèche, en matière minérale, et en matière organique, ainsi que les teneurs en sulfates et en protéines des extraits comprenant au moins un oligomère d’ulvane tel que défini ci-dessus, tels que l’extrait OligoUlvane peuvent être mesurées selon les méthodes suivantes: The contents of dry matter, mineral matter, and organic matter, as well as the sulphate and protein contents of the extracts comprising at least one ulvan oligomer as defined above, such as the OligoUlvane extract can be measured. according to the following methods:
La teneur en matière sèche (MS) correspond au poids obtenu après séchage de la matière brute (MB) pendant 24h à 103°C;  The dry matter content (DM) corresponds to the weight obtained after drying of the raw material (MB) for 24 hours at 103 ° C .;
Les teneurs en matières organique (MO) et minérale (MM) peuvent être quantifiées par gravimétrie après 12h à 550°C;  The contents of organic matter (OM) and mineral (MM) can be quantified by gravimetry after 12 hours at 550 ° C;
La teneur en sulfate (S04) peut être quantifiée selon Quemener et al. (Quemener, B., Lahaye, M., Bobin-Dubigeon, C. (1997) Sugar détermination in ulvans by a chemical-enzymatic method coupled to high performance anion exchange chromatography. Journal of Applied Phycology, 9, 179-188); The sulphate content (SO 4 ) can be quantified according to Quemener et al. (Quemener, B., Lahaye, M., Bobin-Dubigeon, C. (1997) Sugar determination in a chemical-enzymatic method coupled to high performance anion exchange chromatography, Journal of Applied Phycology, 9, 179-188);
La teneur en protéines peut être estimée à partir du dosage d'azote N Kjelhdahl x 6.25; The protein content can be estimated from the N Kjelhdahl x 6.25 nitrogen assay;
La teneur totale en acides uroniques peut être déterminée par méthode colorimétrique, à l'aide du m-phényl phénol (Thibault J. -F. 1979. Automatisation du dosage des substances pectiques par la méthode au meta-hydroxydiphenyl. Lebensm-Wiss. T echnol., 12, pp. 247-251 .), en utilisant l'acide D-glucuronique comme étalon ; The total content of uronic acids can be determined by colorimetric method, using m-phenyl phenol (Thibault J.-F. 1979. Automation of the dosage of pectic substances by the meta-hydroxydiphenyl method Lebensm-Wiss. echnol., 12, pp. 247-251.), using D-glucuronic acid as a standard;
Le profil et la teneur en sucres neutres et acides uroniques peuvent être déterminés par HPLC après méthanolyse acide dans du MeOH-HCI (colonne Absorbosphere RP18, 5 pm, 4 x 250 mm (selon Quemener et al, Food Hydrocolloids, 2000, 14, pp. 9-17). Les pics chromatographiques sont identifiés par comparaison avec des sucres de référence. L’accès à la composition repose d’abord sur une méthanolyse à chaud, afin de rompre les liaisons glycosidiques existantes entre les oses et acides uroniques constitutifs d’un polysaccharide. La réaction aboutit à la formation de 4 à 6 méthylglycosides par sucre constitutif du polymère. Ces composés sont ensuite identifiés et quantifiés par chromatographie en phase liquide, en phase inverse sur colonne C18. L’identification et la quantification sont basées sur la comparaison à des standards de sucres et acides uroniques monomères ayant subi le même traitement de méthanolyse acide. The profile and content of neutral sugars and uronic acids can be determined by HPLC after acid methanolysis in MeOH-HCl (Absorbosphere RP18 column, 5 μm, 4 × 250 mm (according to Quemener et al, Food Hydrocolloids, 2000, 14, pp. Chromatographic peaks are identified by comparison with reference sugars.The access to the composition is based firstly on a hot methanolysis, in order to break the existing glycosidic bonds between the saccharide and the uronic acids constituting the polysaccharide reaction leads to formation from 4 to 6 methyl glycosides per constituent sugar of the polymer. These compounds are then identified and quantified by liquid phase chromatography, reverse phase on a C18 column. The identification and quantification are based on comparison to standards of monomeric uronic sugars and acids having undergone the same acid methanolysis treatment.
Le profil de distribution des poids moléculaires (Mw) des oligomères d’ulvanes dans les extraits de l’invention tels que lOligoUlvane peut être établi par chromatographie HPLC d'exclusion stérique (colonne Shodex SB-806M HQ, volume d'injection: 50 pL, phase mobile: 0,05M NaN03 + 0,02 percent NaN3, débit: 0,5 mL/min, pression: 20 bars, détecteurs: indice de réfraction et UV multi-longueurs d'ondes). The molecular weight distribution profile (Mw) of ulvan oligomers in the extracts of the invention such as OligoUlvane can be established by steric exclusion HPLC chromatography (Shodex SB-806M HQ column, injection volume: 50 μL mobile phase: 0.05M NaNO3 + 0.02 percent NaN3, flow rate: 0.5 mL / min, pressure: 20 bar, detectors: refractive index and UV multi-wavelength).
L'extrait OligoUlvane a de préférence les caractéristiques suivantes (en pourcentages pondéraux): The OligoUlvane extract preferably has the following characteristics (in percentages by weight):
MS (% MB) = 97 %  MS (% MB) = 97%
MO (% MS) = 66,9 %  MO (% MS) = 66.9%
MM (% MS) = 30,1 %  MM (% MS) = 30.1%
Protéines (N x 6,25) (% MS) = 2,95 %  Proteins (N x 6.25) (% MS) = 2.95%
Sucres totaux (équivalent glucose) % = 40,0% Total sugar (glucose equivalent)% = 40.0%
Teneur en sulfate libre = 1 1 ,80 %  Free sulphate content = 1 1, 80%
Teneur en sulfate lié = 7,50 %  Bound sulphate content = 7.50%
Mw (éq. pullulan g/mol) HP-SEC = Bipopulé de 17 000 à 25 000 Da (majoritaire) et de 66 000 à 80 000 Da. Mw (pullulan g / mol) HP-SEC = Bipopulated from 17,000 to 25,000 Da (majority) and from 66,000 to 80,000 Da.
PROCEDE PROCESS
L’invention concerne également un procédé de production d’un extrait comprenant au moins un oligomère d’ulvane tel que défini ci-dessus, comprenant les étapes suivantes : The invention also relates to a method for producing an extract comprising at least one ulvan oligomer as defined above, comprising the following steps:
(i) macération d’algues, en particulier d’algues sèches, de l’ordre des ulvales dans de l'eau pendant une durée d’au moins 30 min, telle que 30 min à 5h, de préférence 1 h à 5h, plus particulièrement de 1 h à 3h telle que 2 h, à une température d’au moins 20°C, notamment entre 45 et 95°C, plus particulièrement entre 70 et 90°C, plus préférentiellement entre 75°C et 85°C telle que 80°C, préférentiellement sous agitation constante, (i) maceration of algae, in particular dry algae, of the order of the ulvals in water for a period of at least 30 minutes, such as 30 minutes to 5 hours, preferably 1 hour to 5 hours, more particularly from 1 hour to 3 hours, such as 2 hours, at a temperature of at least 20 ° C., in particular between 45 and 95 ° C., more particularly between 70 and 90 ° C, more preferably between 75 ° C and 85 ° C such that 80 ° C, preferably with constant stirring,
(ii) hydrolyse dans de l’eau à pH acide notamment à un pH entre 1 et 5, plus particulièrement entre 1 et 4, notamment entre 1 et 3 tel que pH=2 (par ajout d’au moins un acide minéral ou organique, de préférence un acide minéral tel que HCl) pendant une durée d’au moins 30 min telle que 30 min à 15h, de préférence 1 h à 10h, plus particulièrement de 1 h à 4h telle que 3 h à une température d’au moins 20°C, notamment entre 45 et 95°C, plus particulièrement entre 70 et 90°C, plus préférentiellement entre 75°C et 85°C telle que 80°C, préférentiellement sous agitation constante ; puis  (ii) hydrolysis in water at acidic pH, in particular at a pH between 1 and 5, more particularly between 1 and 4, in particular between 1 and 3 such that pH = 2 (by addition of at least one mineral or organic acid , preferably a mineral acid such as HCl) for a period of at least 30 min such as 30 min to 15 h, preferably 1 h to 10 h, more particularly 1 h to 4 h, such as 3 h at a temperature of at least 20 ° C, in particular between 45 and 95 ° C, more particularly between 70 and 90 ° C, more preferably between 75 ° C and 85 ° C such that 80 ° C, preferably with constant stirring; then
(iii) neutralisation à pH 7 par ajout d’au moins une base organique et/ou minérale, de préférence par ajout d’une base minérale forte, telle que NaOH ;  (iii) neutralization at pH 7 by addition of at least one organic and / or mineral base, preferably by addition of a strong mineral base, such as NaOH;
(iv) éventuellement refroidissement;  (iv) optionally cooling;
(v) élimination des insolubles par filtration;  (v) removal of insolubles by filtration;
(vi) éventuellement purification ;  (vi) optionally purification;
(vii) éventuellement refroidissement jusqu’à température ambiante,  (vii) optionally cooling to room temperature,
(viii) éventuellement atomisation, ou lyophilisation.  (viii) optionally atomization, or lyophilization.
L’invention concerne également un procédé de production d’un extrait selon l’invention, comprenant les étapes suivantes : The invention also relates to a method for producing an extract according to the invention, comprising the following steps:
(i) macération d’algues, en particulier d’algues sèches, de l’ordre des ulvales dans de l'eau pendant une durée d’au moins 30 min telle que 30 min à 5h, de préférence 1 h à 5h, plus particulièrement de 1 h à 3h telle que 2 h, à une température d’au moins 20°C, notamment entre 45 et 95°C, plus particulièrement entre 70 et 90°C, plus préférentiellement entre 75°C et 85°C telle que 80°C, préférentiellement sous agitation constante,  (i) maceration of algae, in particular dry algae, of the order of the ulvals in water for a period of at least 30 minutes such as 30 minutes to 5 hours, preferably 1 hour to 5 hours, plus especially from 1 hour to 3 hours, such as 2 hours, at a temperature of at least 20 ° C., in particular from 45 ° to 95 ° C., more particularly from 70 ° to 90 ° C., more preferably from 75 ° to 85 ° C. than 80 ° C, preferably with constant stirring,
(ii) hydrolyse dans de l’eau à pH acide notamment à un pH entre 1 et 5, plus particulièrement entre 1 et 4, notamment entre 1 et 3 tel que pH 2 (par ajout d’au moins un acide minéral ou organique, de préférence un acide minéral tel que HCl) pendant une durée d’au moins 30 min telle que 30 min à 15h, de préférence 1 h à 10h, plus particulièrement de 1 h à 4h telle que 3 h à une température d’au moins 20°C, notamment entre 45 et 95°C, plus particulièrement entre 70 et 90°C, plus préférentiellement entre 75°C et 85°C telle que 80°C, préférentiellement sous agitation constante ; puis (iii) neutralisation à pH 7 par ajout d’au moins une base organique et/ou minérale, de préférence par ajout d’une base minérale forte, telle que NaOH ; (ii) hydrolysis in water at acidic pH, in particular at a pH between 1 and 5, more particularly between 1 and 4, in particular between 1 and 3 such as pH 2 (by addition of at least one mineral or organic acid, preferably a mineral acid such as HCl) for a duration of at least 30 min such as 30 min to 15 h, preferably 1 h to 10 h, more particularly 1 h to 4 h such as 3 h at a temperature of at least 20 ° C, especially between 45 and 95 ° C, more particularly between 70 and 90 ° C, more preferably between 75 ° C and 85 ° C such that 80 ° C, preferably with constant stirring; then (iii) neutralization at pH 7 by addition of at least one organic and / or mineral base, preferably by addition of a strong mineral base, such as NaOH;
(iv) éventuellement refroidissement,  (iv) optionally cooling,
(v) clarification,  (v) clarification,
(vi) filtration stérilisante,  (vi) sterilizing filtration,
(vii) atomisation ou lyophilisation.  (vii) atomization or lyophilization.
De préférence, dans le procédé de l’invention, les algues utilisées sont des Ulva lactuca. Preferably, in the process of the invention, the algae used are Ulva lactuca.
De préférence l’étape (i) a lieu à une température d’environ 80°C. Par « macération », on entend une étape qui consiste à laisser séjourner l’algue ou un extrait d’algue dans un liquide non porté à ébullition. Cette étape permet d’extraire les composés solubles des algues.  Preferably step (i) takes place at a temperature of about 80 ° C. By "maceration" is meant a step of letting the algae or seaweed extract remain in a liquid that is not boiled. This step makes it possible to extract the soluble compounds from the algae.
De préférence l’étape (ii) a lieu à une température d’environ 80°C. De préférence le pH de la solution à cette étape est compris entre 1 et 3, en particulier le pH est de 2. Le pH acide de la solution peut être obtenu par ajout de HCl.  Preferably step (ii) takes place at a temperature of about 80 ° C. Preferably the pH of the solution at this stage is between 1 and 3, in particular the pH is 2. The acidic pH of the solution can be obtained by adding HCl.
De préférence pour l’étape (iii) on utilise NaOH comme base forte.  Preferably for step (iii), NaOH is used as the strong base.
L’étape de clarification peut être réalisée par une étape ou par une succession de sous-étapes d’essorages et de filtrations. De préférence l’étape de clarification permet d’obtenir une solution exempte de particules de plus de 0,5 pm.  The clarification step may be carried out by a step or by a succession of sub-stages of spin-offs and filtrations. Preferably, the clarification step makes it possible to obtain a solution free of particles of more than 0.5 μm.
L’étape de filtration stérilisante est une étape bien connue de l’homme du métier. The sterilizing filtration step is a step well known to those skilled in the art.
L’étape de purification peut être réalisée par une succession de sous-étapes permettant la séparation de l’oligomère voulu des autres composés de la solution. Cette étape peut notamment comprendre une étape de séparation par chromatographie, centrifugation, extraction et/ou cristallisation. The purification step can be carried out by a succession of sub-steps allowing the separation of the desired oligomer from the other compounds of the solution. This step may in particular comprise a separation step by chromatography, centrifugation, extraction and / or crystallization.
De préférence les produits obtenus par les procédés selon l’invention sont conservés au sec et au froid, plus préférentiellement entre 0 et 10°C et de préférence à environ 4°C.  Preferably, the products obtained by the processes according to the invention are kept dry and cold, more preferably between 0 and 10 ° C. and preferably at about 4 ° C.
L’invention concerne également un oligomère d’ulvane susceptible d’être obtenu par le procédé de production d’un extrait comprenant au moins un oligomère d’ulvane selon l’invention.  The invention also relates to an ulvan oligomer that can be obtained by the process for producing an extract comprising at least one ulvan oligomer according to the invention.
L’invention concerne en outre un extrait comprenant au moins un oligomère d’ulvane susceptible d’être obtenu par le procédé de production d’un extrait comprenant au moins un oligomère d’ulvane selon l’invention. COMPOSITION The invention further relates to an extract comprising at least one ulvan oligomer obtainable by the process for producing an extract comprising at least one ulvan oligomer according to the invention. COMPOSITION
L’invention a également pour objet une composition notamment cosmétique contenant au moins un oligomère d’ulvane tel que défini ci-dessus et/ou un extrait selon l’invention.  The invention also relates to a particularly cosmetic composition containing at least one ulvan oligomer as defined above and / or an extract according to the invention.
L’invention concerne également une composition notamment cosmétique susceptible d’être obtenue par le procédé de production d’un extrait comprenant au moins un oligomère d’ulvane selon l’invention. The invention also relates to a particularly cosmetic composition that can be obtained by the process for producing an extract comprising at least one ulvan oligomer according to the invention.
L’invention concerne aussi une utilisation cosmétique non-thérapeutique d’une composition selon l’invention pour assouplir et/ou diminuer le tiraillement de la peau. The invention also relates to a non-therapeutic cosmetic use of a composition according to the invention for softening and / or reducing the tightness of the skin.
L’invention concerne ainsi l’utilisation cosmétique non-thérapeutique d’au moins un oligomère d’ulvane tel que défini ci-dessus ou d’un extrait tels que défini ci-dessus ou d’une composition cosmétique telle que définie ci-dessus pour assouplir et/ou diminuer le tiraillement de la peau. The invention thus relates to the non-therapeutic cosmetic use of at least one ulvan oligomer as defined above or an extract as defined above or a cosmetic composition as defined above to soften and / or reduce the tightness of the skin.
Par « peau», on entend la peau humaine et/ou le cuir chevelu humain. Par peau, on entend en particulier la peau du corps, en particulier des jambes, des bras, des mains, du cou et la peau du visage. By "skin" is meant human skin and / or human scalp. By skin is meant in particular the skin of the body, especially the legs, arms, hands, neck and the skin of the face.
Par « assouplir » la peau, on entend ici augmenter la souplesse, la flexibilité ou l’élasticité de la peau, et/ou augmenter la douceur de la peau, et/ou limiter l’apparition de rides et ridules.  By "softening" the skin, it is intended herein to increase the suppleness, flexibility or elasticity of the skin, and / or to increase the softness of the skin, and / or to limit the appearance of wrinkles and fine lines.
Par « diminuer le tiraillement de la peau» on entend diminuer la tension et les sensations d’inconfort qui peuvent y être liées. Ce type de sensations est souvent lié aux types de peaux sensibles comme les peaux sèches et/ou âgées.  By "decrease the tension of the skin" is meant to reduce the tension and feelings of discomfort that may be related. This type of sensations is often related to sensitive skin types such as dry and / or aged skin.
Selon un mode de réalisation, la composition utilisée selon l'invention ou l’extrait utilisé selon l'invention, comprend entre 0,01 et 20% d’oligomère(s) d’ulvane tel que défini ci-dessus plus particulièrement entre 0,5 et 10%, plus particulièrement entre 1 et 7% en poids par rapport au poids sec de la composition. According to one embodiment, the composition used according to the invention or the extract used according to the invention comprises between 0.01 and 20% ulvan oligomer (s) as defined above more particularly between 0. , 5 and 10%, more particularly between 1 and 7% by weight relative to the dry weight of the composition.
Selon un mode de réalisation, la composition selon l'invention ou l’extrait selon l'invention peut être utilisé(e) chez un sujet ayant une peau sensible et en particulier une peau sèche et/ou âgée. Selon un mode de réalisation, la composition selon l'invention ou l’extrait selon l'invention peut être utilisé(e) chez un sujet ayant un cuir chevelu sec. According to one embodiment, the composition according to the invention or the extract according to the invention can be used in a subject having a sensitive skin and in particular a dry and / or aged skin. According to one embodiment, the composition according to the invention or the extract according to the invention can be used in a subject having a dry scalp.
De préférence la composition utilisée selon l'invention ou l’extrait utilisé selon l'invention est destiné à une application topique.  Preferably the composition used according to the invention or the extract used according to the invention is intended for topical application.
Les compositions utilisées selon l'invention contiennent préférentiellement un milieu physiologiquement acceptable, c'est-à-dire compatible avec la peau. Ce milieu physiologiquement acceptable peut être plus particulièrement constitué d'eau et éventuellement d'un solvant organique physiologiquement acceptable choisi par exemple parmi les alcools inférieurs comportant de 1 à 8 atomes de carbone et en particulier de 1 à 6 atomes de carbone, comme l'éthanol, l'isopropanol, le propanol, le butanol; les polyéthylène glycols ayant de 6 à 80 unités oxyde d'éthylène et les polyols comme le propylène glycol, l'isoprène glycol et le butylène glycol.  The compositions used according to the invention preferentially contain a physiologically acceptable medium, that is to say compatible with the skin. This physiologically acceptable medium may more particularly consist of water and optionally of a physiologically acceptable organic solvent chosen, for example, from lower alcohols containing from 1 to 8 carbon atoms and in particular from 1 to 6 carbon atoms, such as ethanol, isopropanol, propanol, butanol; polyethylene glycols having from 6 to 80 ethylene oxide units and polyols such as propylene glycol, isoprene glycol and butylene glycol.
Ladite composition peut notamment se présenter sous forme d'une crème ou de lotion, par exemple d'application journalière, d'un savon liquide ou solide, d’un gel douche, d'un masque traitant, d’un patch, d’un shampooing, d’un après-shampooing, d'une lotion ou d'un gel.  Said composition may especially be in the form of a cream or lotion, for example of daily application, a liquid or solid soap, a shower gel, a mask treatment, a patch, a shampoo, a conditioner, a lotion or a gel.
La composition selon l'invention ou l’extrait selon l'invention peut également être utilisé(e) pour hydrater la peau. The composition according to the invention or the extract according to the invention can also be used to moisturize the skin.
Les quantités des différents constituants du milieu physiologique de la composition selon l'invention sont celles généralement utilisées dans les domaines considérés. En outre, ces compositions sont préparées selon les méthodes usuelles.  The amounts of the various constituents of the physiological medium of the composition according to the invention are those generally used in the fields under consideration. In addition, these compositions are prepared according to the usual methods.
De préférence, la composition est utilisée selon l’invention comme agent actif à une quantité efficace, c’est-à-dire à une quantité lui permettant d’avoir l’effet désiré.  Preferably, the composition is used according to the invention as active agent at an effective amount, that is to say at a quantity allowing it to have the desired effect.
Selon un mode de réalisation, la composition utilisée comprend entre 2 et 15% en poids par rapport au poids total de la composition, d’extrait comprenant au moins un oligomère d'ulvane tel que défini ci-dessus. According to one embodiment, the composition used comprises between 2 and 15% by weight relative to the total weight of the composition, extract comprising at least one ulvan oligomer as defined above.
La composition de l’invention est de préférence une composition aqueuse. The composition of the invention is preferably an aqueous composition.
La composition peut comprendre en outre au moins un adjuvant, notamment des adjuvants usuellement employés dans le domaine cosmétique, et notamment choisis parmi les huiles; les cires, les pigments, les charges, les colorants, les tensioactifs, les émulsionnants ; les actifs cosmétiques, les filtres UV, les polymères, les épaississants, les polymères filmogènes, les conservateurs, les parfums, les bactéricides, les absorbeurs d'odeur, les antioxydants. The composition may furthermore comprise at least one adjuvant, especially adjuvants conventionally employed in the cosmetics field, and especially chosen from oils; waxes, pigments, fillers, dyes, surfactants, emulsifiers; cosmetic active ingredients, UV filters, polymers, thickeners, film-forming polymers, preservatives, perfumes, bactericides, odor absorbers, antioxidants.
Les quantités de ces différents adjuvants sont celles classiquement utilisées dans le domaine considéré, et par exemple de 0,01 à 20 % du poids total de la composition. The amounts of these various adjuvants are those conventionally used in the field under consideration, and for example from 0.01 to 20% of the total weight of the composition.
L’invention se rapporte également à un procédé cosmétique d’assouplissement et/ou de diminution du tiraillement de la peau comprenant une étape d’application topique, d’une quantité efficace d’une composition selon l’invention ou d’un extrait selon l’invention. The invention also relates to a cosmetic process for softening and / or reducing skin tightness comprising a topical application step, an effective amount of a composition according to the invention or an extract according to the invention. the invention.
Dans la description et dans les exemples suivants, sauf indication contraire, les pourcentages sont des pourcentages en poids et les plages de valeurs libellées sous la forme "entre ... et ...", « allant de ... à ... », ou « supérieur à ... » incluent les bornes précisées. In the following description and examples, unless otherwise indicated, percentages are percentages by weight and ranges of values in the form "between ... and ...", "ranging from ... to ... ", Or" greater than ... "include the specified boundaries.
Dans toute la demande, le libellé "comprenant un" ou "comportant un" signifie "comprenant au moins un" ou "comportant au moins" un sauf si le contraire est spécifié.  Throughout the application, the wording "comprising a" or "comprising a" means "comprising at least one" or "comprising at least" one unless the contrary is specified.
Les exemples ci-après sont présentés à titre illustratif et non limitatif du domaine de l’invention. The following examples are presented by way of illustration and not limitation of the field of the invention.
EXEMPLES EXAMPLES
Exemple 1 : préparation d’un extrait OliqoUlvane Example 1 Preparation of an OliqoUlvane Extract
164 g de poudre d’algues Ulva lactuca sont utilisés pour faire un solution aqueuse à 5%. La solution aqueuse à 5% est chauffée à 80°C pendant 2 heures sous agitation constante. On ajoute alors une solution aqueuse d’acide chlorhydrique 2N à la solution obtenue à 80°C jusqu’à pH = 2 puis on maintient sous agitation pendant 4h à 80°C. Le milieu est alors neutralisé à 80°C par ajout d’une solution aqueuse de soude 2N jusqu’à pH = 7 avant d’être refroidi à 40°C, puis filtré et essoré. Le filtrat est clarifié jusqu’à stérilisation (à 0,2 microns) puis atomisé. 164 g of Ulva lactuca seaweed powder is used to make a 5% aqueous solution. The 5% aqueous solution is heated at 80 ° C. for 2 hours with constant stirring. An aqueous solution of 2N hydrochloric acid is then added to the solution obtained at 80 ° C. until pH = 2, and then the mixture is stirred for 4 hours at 80 ° C. The medium is then neutralized at 80 ° C. by adding an aqueous solution of 2N sodium hydroxide until pH = 7 before being cooled to 40 ° C., and then filtered and drained. The filtrate is clarified until sterilization (at 0.2 microns) and then atomized.
On obtient ainsi après atomisation 18,3 g d’extrait OligoUlvane.  18.3 g of OligoUlvane extract are thus obtained after atomization.
Cet extrait est conservé à 4°C à l’abri de l’air et de l’humidité. Les analyses réalisées sur l’extrait atomisé obtenu ont donné les résultats suivants : This extract is stored at 4 ° C away from air and moisture. The analyzes carried out on the atomized extract obtained gave the following results:
Matière sèche (% extrait) = 97 % Dry matter (% extract) = 97%
Matières organiques (% matière sèche) = 66,9 %  Organic matter (% dry matter) = 66.9%
MM (% matière sèche) = 30,1 %  MM (% dry matter) = 30.1%
Na (% matière sèche) = 1 1 ,38 %  Na (% dry matter) = 1 1, 38%
Protéines (N x 6,25) (% matière sèche) = 2,95 %  Proteins (N x 6.25) (% dry matter) = 2.95%
Sucres totaux (équivalent glucose) % matière sèche = 40,0%  Total sugar (glucose equivalent)% dry matter = 40.0%
Teneur en sulfate libre = 1 1 ,80 %  Free sulphate content = 1 1, 80%
Teneur en sulfate lié = 7,50 %  Bound sulphate content = 7.50%
Mw (éq. pullulan g/mol) HP-SEC = Bipopulé de 17 000 à 25 000 Da (majoritaire) et de 66 000 à 80 000 Da. Mw (pullulan g / mol) HP-SEC = Bipopulated from 17,000 to 25,000 Da (majority) and from 66,000 to 80,000 Da.
Exemple 2 : Evaluation de l'assouplissement mécanique du stratum corneum Example 2 Evaluation of the mechanical relaxation of the stratum corneum
L’appareil de DMA (Dynamic Mechanical Analysis) vendu sous la référence ElectroForce ® 3100 par la société Bose a été utilisé. The DMA (Dynamic Mechanical Analysis) apparatus sold under the reference ElectroForce® 3100 by the company Bose was used.
Cette technique permet d'étudier les propriétés viscoélastiques du stratum corneum. Le matériau est sollicité sinusoïdalement et sa déformation est mesurée. Le module de conservation (E') du stratum corneum peut ainsi être déterminé. Le module de conservation permet de caractériser mécaniquement le stratum corneum. Cette grandeur est directement liée aux propriétés élastiques du stratum corneum. L'impact de plusieurs saccharides sulfatés sur ce module de conservation a été étudié, notamment l’extrait OligoUlvane de l’exemple 1 et deux autres compositions qui ont été préparées selon le protocole décrit dans la demande de brevet FR2982152 à partir d’Ulva Rotundata et d’Ulva Armoricana. This technique makes it possible to study the viscoelastic properties of the stratum corneum. The material is sinusoidally stressed and its deformation is measured. The conservation module (E ') of the stratum corneum can thus be determined. The conservation module makes it possible to characterize the stratum corneum mechanically. This size is directly related to the elastic properties of the stratum corneum. The impact of several sulphated saccharides on this conservation module has been studied, notably the OligoUlvane extract of Example 1 and two other compositions which have been prepared according to the protocol described in patent application FR2982152 from Ulva Rotundata. and Ulva Armoricana.
Préparation des échantillons et Protocole : Sample Preparation and Protocol:
La surface de l'échantillon de Stratum Corneum à tester est de 2 cm2 (1 cm c 2 cm). Les échantillons ont été préalablement conditionnés à 75 % d'humidité relative pendant minimum 12 heures, et la mesure a été également réalisée à 75 % d'humidité relative. Des solutions de matières premières à 5 % en masse (extrait sec) ont été préparées dans l'eau et 10 mI/cm2 ont été déposés sur chaque échantillon de stratum corneum. La solution a été étalée sur le stratum corneum de manière à recouvrir la surface entière. The surface of the Stratum Corneum sample to be tested is 2 cm 2 (1 cm c 2 cm). The samples were preconditioned at 75% relative humidity for a minimum of 12 hours, and the measurement was also carried out at 75% relative humidity. Solutions of raw materials at 5% by mass (dry extract) were prepared in water and 10 mI / cm 2 were deposited on each stratum corneum sample. The solution was spread on the stratum corneum so as to cover the entire surface.
L'amplitude dynamique de sollicitation a été réglée à 40 pm, ce qui correspond à une déformation dans le domaine élastique du stratum corneum (0,2 % de déformation). Chaque échantillon a été sollicité à la fréquence de 10 Hz, selon la plus grande longueur. Des échantillons de stratum corneum provenant de plusieurs donneurs ont été utilisés pour vérifier que les résultats sont cohérents et répétables.  The dynamic amplitude of stress was set at 40 μm, which corresponds to a deformation in the elastic domain of the stratum corneum (0.2% deformation). Each sample was solicited at the frequency of 10 Hz, according to the greatest length. Stratum corneum samples from several donors were used to verify that the results are consistent and repeatable.
La variation du module élastique de chaque échantillon est calculée à partir de la mesure du module élastique de l'échantillon traité au bout de deux heures de séchage et d’absorption de la solution, (E’2h) par rapport à celle du même échantillon avant traitement à t=0 (EΌ).  The variation of the elastic modulus of each sample is calculated from the measurement of the elastic modulus of the treated sample after two hours of drying and absorption of the solution, (E'2h) with respect to that of the same sample. before treatment at t = 0 (EΌ).
DE’ = (E’2h-E’0) / EΌ  DE '= (E'2h-E'0) / EΌ
Les valeurs moyennes obtenues sont présentées dans le tableau ci-après. Ce test démontre les variations de propriétés mécaniques du stratum corneum, qui sont liées avec la sensation de confort après l'application de polysaccharide sur la peau. Un saccharide qui rigidifie le stratum corneum (DE’ positive) sera perçu comme inconfortable sur la peau, donnant lieu aux sensations de tiraillement et de la peau rigide. A l’inverse, un saccharide assouplissant (DE’ négative) apportera un bénéfice cosmétique sous forme de peau plus élastique, plus souple donc une sensation de confort.  The average values obtained are presented in the table below. This test demonstrates the variations in mechanical properties of the stratum corneum, which are related to the sensation of comfort after the application of polysaccharide on the skin. A saccharide that stiffens the stratum corneum (DE 'positive) will be perceived as uncomfortable on the skin, giving rise to feelings of tugging and rigid skin. Conversely, a softening saccharide (DE 'negative) will bring a cosmetic benefit in the form of more elastic skin, more flexible therefore a feeling of comfort.
Tableau 1 : Table 1:
Figure imgf000019_0001
Parmi les saccharides sulfatés testés, l’extrait OligoUlvane de l’invention a l’effet assouplissant le plus fort, proche de la référence positive (le glycérol).
Figure imgf000019_0001
Among the sulphated saccharides tested, the OligoUlvane extract of the invention has the strongest softening effect, close to the positive reference (glycerol).
Exemple 3 : composition cosmétique (% pondéraux) Example 3: Cosmetic composition (% by weight)
Extrait OligoUlvane de l’exemple 1 6%  OligoUlvane extract of Example 1 6%
- Carbomer 1 %  - Carbomer 1%
- Eau qsp100  - Water qsp100
- Conservateur qsp  - Conservative qs
Cette composition peut être appliquée quotidiennement sur le corps.  This composition can be applied daily on the body.

Claims

REVENDICATIONS
1.- Extrait comprenant au moins un oligomère d’ulvane ayant un poids moléculaire compris entre 5 000 Da et 90 000 Da. 1.- Extract comprising at least one ulvan oligomer having a molecular weight between 5,000 Da and 90,000 Da.
2.- Extrait selon la revendication 1 présentant deux populations d’oligomères d’ulvanes de poids moléculaires différents, dans lequel la première population a un poids moléculaire compris entre 17 000 Da et 25 000 Da et la deuxième population a un poids moléculaire compris entre 66 000 Da et 80 000 Da. 2. The extract of claim 1 having two populations of ulvan oligomers of different molecular weights, wherein the first population has a molecular weight between 17,000 Da and 25,000 Da and the second population has a molecular weight between 66,000 Da and 80,000 Da.
3.- Extrait selon l’une quelconque des revendications 1 à 2 dans lequel l’extrait provient d’Ulva lactuca. 3. Extract according to any one of claims 1 to 2 wherein the extract is from Ulva lactuca.
4.- Extrait selon l’une quelconque des revendications 1 à 3, dans lequel le taux de sulfates greffés est compris entre 4% et 15%, par rapport au poids sec de l’extrait. 4. Extract according to any one of claims 1 to 3, wherein the level of grafted sulphates is between 4% and 15%, relative to the dry weight of the extract.
5.- Extrait selon la revendication 4, dans lequel le taux de sulfates greffés est de 7,5%, par rapport au poids sec de l’extrait. 5. Extract according to claim 4, wherein the level of grafted sulphates is 7.5%, relative to the dry weight of the extract.
6.- Extrait selon l’une quelconque des revendications 1 à 5, dans lequel les oligomères d’ulvanes contenus dans l’extrait comprennent 24,4% de rhamnose, 10,6% d’acide glucuronique, 12,1% d’acide iduronique, 3,5% de xylose, 2,4% de galactose et 5,7% de glucose, par rapport au poids sec de l’extrait. 6. Extract according to any one of claims 1 to 5, in which the oligomers of ulvans contained in the extract comprise 24.4% of rhamnose, 10.6% of glucuronic acid, 12.1% of iduronic acid, 3.5% xylose, 2.4% galactose and 5.7% glucose, based on the dry weight of the extract.
7.- Extrait selon la revendication 6, dans lequel le taux de matière organique est de 66,90%, le taux de matière minérale est de 30,1 %, le taux de Na est de 1 1 ,38%, le taux de protéine est de 2,95%, le taux de sucres totaux (équivalent glucose) est de 40%, le taux de sulfate libre est de 1 1 ,8% et le taux de sulfates greffés est de 7,5%, par rapport au poids sec de l’extrait. 7. Extract according to claim 6, wherein the organic matter content is 66.90%, the mineral matter content is 30.1%, the Na content is 1 1, 38%, the protein is 2.95%, the total sugar level (glucose equivalent) is 40%, the free sulfate level is 1 1, 8% and the level of sulfates grafted is 7.5%, compared to dry weight of the extract.
8.- Composition contenant au moins un oligomère d’ulvane tel que défini dans la revendication 1 et/ou un extrait selon l’une quelconque des revendications 1 à 7. 8. A composition containing at least one ulvan oligomer as defined in claim 1 and / or an extract according to any one of claims 1 to 7.
9.- Procédé de production d’un extrait tel que défini dans l’une quelconque des revendications 1 à 7, comprenant les étapes suivantes : (i) macération d’algues sèches de l’ordre des ulvales dans de l'eau pendant au moins 30 min, à une température d’au moins 20°C, préférentiellement sous agitation constante, 9. A process for producing an extract as defined in any one of claims 1 to 7, comprising the following steps: (i) maceration of dry algae in water for at least 30 minutes, at a temperature of at least 20 ° C, preferably with constant stirring,
(ii) hydrolyse dans de l’eau à pH acide pendant au moins 30 min à une température d’au moins 20°C, préférentiellement sous agitation constante, puis (ii) hydrolysis in water at acidic pH for at least 30 min at a temperature of at least 20 ° C, preferably with constant stirring, then
(iii) neutralisation à pH 7 par ajout d’au moins une base organique et/ou minérale,(iii) neutralization at pH 7 by addition of at least one organic and / or mineral base,
(iv) éventuellement refroidissement, (iv) optionally cooling,
(v) clarification,  (v) clarification,
(vi) filtration stérilisante,  (vi) sterilizing filtration,
(vii) atomisation, ou lyophilisation.  (vii) atomization, or lyophilization.
10.- Extrait comprenant au moins un oligomère d’ulvane susceptible d’être obtenu par le procédé de production selon la revendication 9. 10.- extract comprising at least one ulvan oligomer obtainable by the production method according to claim 9.
1 1.- Composition cosmétique comprenant au moins un oligomère d’ulvane et/ou un extrait selon l’une quelconque des revendications 1 à 7. 1. Cosmetic composition comprising at least one ulvan oligomer and / or an extract according to any one of claims 1 to 7.
12.- Utilisation cosmétique non-thérapeutique d’au moins un oligomère d’ulvanes tel que défini dans la revendication 1 ou d’un extrait selon l’une quelconque des revendications 1 à 7 ou d’une composition selon la revendication 1 1 pour assouplir et/ou diminuer le tiraillement de la peau. 12. Non-therapeutic cosmetic use of at least one oligomer of ulvans as defined in claim 1 or an extract according to any one of claims 1 to 7 or a composition according to claim 1 for soften and / or reduce the tightness of the skin.
13.- Utilisation cosmétique non-thérapeutique selon la revendication 12, dans laquelle la concentration d’oligomères d'ulvane de la composition ou de l’extrait est comprise entre 0,01% et 20% d’oligomères d’ulvanes en poids par rapport au poids sec de la composition ou de l’extrait respectivement. 13. Non-therapeutic cosmetic use according to claim 12, in which the concentration of ulvan oligomers of the composition or of the extract is between 0.01% and 20% of ulvan oligomers by weight per relative to the dry weight of the composition or extract respectively.
14.- Procédé cosmétique d’assouplissement et/ou de diminution du tiraillement de de la peau comprenant une étape d’application topique, d’une quantité efficace d’une composition selon la revendication 1 1 ou d’un extrait selon l’une quelconque des revendications 1 à 7. 14. Cosmetic process for softening and / or reducing the tightness of the skin, comprising a step of topical application, an effective amount of a composition according to claim 1 or an extract according to one of the following: any of claims 1 to 7.
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