WO2009109946A1

WO2009109946A1 - Cosmetic treatment process based on fruit or vegetable polyphenols

Info

Publication number: WO2009109946A1
Application number: PCT/IB2009/050942
Authority: WO
Inventors: Jean-François Grollier; Laurence Garnier; Boudiaf Boussouira
Original assignee: L'oreal
Priority date: 2008-03-07
Filing date: 2009-03-06
Publication date: 2009-09-11
Also published as: FR2928263B1; FR2928263A1; EP2249793A1

Abstract

The present invention relates to a cosmetic process for treating keratin materials, comprising the topical application to the said materials of at least one cosmetic composition, which is free of polyphenol oxidase and which comprises at least one polyphenol in combination with at least one sugar and possibly also one fruit acid, the said polyphenol,sugar and possibly fruit acid being derived from fruit or vegetables.

Description

Cosmetic treatment process based on fruit or vegetable polyphenols

The present invention relates to a cosmetic process for treating keratin materials, comprising the topical application to the said materials of at least one polyphenol in combination with at least one sugar, derived from fruit and/or vegetables. The invention also relates to a corresponding cosmetic or dermato logical composition and to an associated cosmetic assembly.

Polyphenols are naturally present in large amount in the plant kingdom. As illustrations of plant varieties that are particularly rich in polyphenols, mention may be made especially of green tea, apple, lychee, grape and pine bark. Thus, 37 phenolic compounds, the most abundant of which are chlorogenic acid, procyanidins Bl and B2, epicatechin, phloretin, phloridzin (glycosyl derivative of phloretin) and p-coumaric acid, have been characterized in apple.

In general, these polyphenols have particularly advantageous physiological properties, such as antioxidant, antimutagenic, antiallergic, anticancer and antidiabetic properties.

Consequently, a certain number of cosmetic and/or pharmaceutical compositions containing polyphenols have already been proposed.

Thus, document FR 2 814 943 proposes a composition for colouring the skin and/or keratin materials, especially containing dye precursors of polyphenol type extracted from fruit such as apples, grapes or bananas, or from vegetables such as potatoes.

Document JP 2000-344 655 proposes to combine an extract of a plant (for example strawberry, apple, grape and their seeds, or beans) containing polyphenols with a parsley extract to obtain a cosmetic product for the skin that has improved antioxidant activity.

Document FR 2 851 916 itself describes compositions for promoting the natural pigmentation of the skin or its integuments, containing catechol polyphenols used in the form of a plant extract.

It should be noted that the polyphenols under consideration in these compositions of the prior art are generally used in a purified form, i.e. not combined with additional substances. Usually, these polyphenols are obtained by extraction of plants.

Thus, document EP 1 243 586 Bl proposes cosmetic compositions containing a dihydrochalcone-rich phenolic fraction obtained by extraction of ripe apples. Document EP-A-O 657 169 Al also describes the production of a polyphenolic fraction for therapeutic purposes, obtained from apples, via steps of pressing and/or extraction and purification. The polyphenolic fraction thus obtained is composed exclusively of polyphenolic compounds. Furthermore, purified forms of polyphenols are also commercially available.

As illustrations of these commercial polyphenolic extracts, mention may be made especially of the products APPL'IN™ from the company Diana Naturals or Pomactiv^® from the company VaI de Vire.

The present invention is also directed towards exploiting the advantageous properties of polyphenols in the cosmetic or dermatological field and more particularly for increasing their cosmetic or dermatological efficacy.

Moreover, it is directed towards satisfying the passion of users for "natural" cosmetic products, i.e. products that essentially use natural components. For the purposes of the invention, the term "natural component" means a component found in its native form in nature, forming part of the plant, animal, fossil or mineral kingdom, and which is not the result of an industrial treatment, as opposed to an artificial, manufactured, industrial or synthetic component.

Specifically, users nowadays expect cosmetic or dermatological compositions to be of reinforced ecological nature, in particular to have constituents that are, as far as possible, biorenewable raw materials.

For the purposes of the invention, the term "biorenewable raw material" means a raw material forming part of the plant or animal kingdom, which is infinitely renewable by simple plant or animal production.

However, for obvious reasons, the use of biorenewable raw materials such as extracts of fruit or vegetables is not without additional problems, especially in terms of the galenical formulation and/or stability over time.

Against all expectation, the inventors have discovered that it is possible to satisfy all these expectations, with the proviso of using these polyphenols in a specific form. The inventors have found, unexpectedly, that the use of at least one polyphenol together with at least one sugar proves to be particularly beneficial in terms of cosmetic properties. What is more, such combinations have the further advantage of being extractable from the same biorenewable source and in particular from a fruit or vegetable.

Thus, according to one of its aspects, the invention relates to a cosmetic process for treating keratin materials, comprising the topical application to the said materials of at least one cosmetic composition, which is free of polyphenol oxidase and which comprises at least one polyphenol in combination with at least one sugar, the said polyphenol and the said sugar being derived from fruit or vegetables, with the said polyphenol being present in a proportion of less than 75% by weight expressed as gallic acid equivalent relative to the weight of the said composition, and the presence of the said sugar being detectable in the said composition via acid hydrolysis.

It is known that the acid hydrolysis of sugar(s) leads to the formation of sugar degradation derivatives and in particular to the formation of ethoxymethylfurfural, the qualitative or quantitative characterization of which falls within the competence of a person skilled in the art. According to another of its aspects, the invention relates to a cosmetic process for treating keratin materials, comprising the topical application to the said materials of at least one cosmetic composition, which is free of polyphenol oxidase and which comprises at least one polyphenol in combination with at least one sugar, the said polyphenol and the said sugar being derived from fruit or vegetables and being used in a polyphenol(s)/sugar(s) weight ratio of less than or equal to 5, in particular less than or equal to 3, advantageously less than or equal to 1 and even more advantageously less than or equal to 0.5.

According to another of its aspects, the invention relates to a cosmetic process for treating keratin materials, comprising the topical application to the said materials of at least one cosmetic composition, which is free of polyphenol oxidase, the said composition comprising at least one polyphenol in combination with at least one sugar, the said polyphenol and the said sugar being derived from fruit or vegetables, and the said sugar being present in a content of from 5% to 60% by weight relative to the total weight of the said composition. According to one particular embodiment, the cosmetic composition of the process of the invention may also comprise at least one fruit acid derived from fruit or vegetables. Fruit acids are molecules present in many fruit or vegetables, such as apple, lemon, orange, redcurrant, almond, etc.

They are mainly α-hydroxy acids, also known by the abbreviation AHA.

In general, on account of their hygroscopicity, fruit acids have advantageous properties in terms of skin moisturization.

In addition, α-hydroxy acids are generally used in cosmetic compositions, as agents for combating ageing of the skin, in particular by promoting desquamation, i.e. the removal of "dead" cells located at the surface of the horny layer of the epidermis.

Fruit acids may, for example, prove to be particularly useful for treating greasy skin, for which an excess of sebum leads to a slo wing-down of the desquamation of dead cells, resulting in thickening of the epidermis.

According to one embodiment, the cosmetic treatment process according to the invention may jointly comprise the oral administration of at least one polyphenol in combination or otherwise with at least one sugar. The cosmetic treatment process may thus, for example, be accompanied by a topical application of a composition in accordance with the invention and of an oral administration of at least one polyphenol in combination or otherwise with at least one sugar. The polyphenols administered orally may be used at doses of from 0.5 to 2000 mg/day, especially from 10 to 1000 mg/day and preferably from 20 to 300 mg/day. According to one preferred embodiment variant, the polyphenol in combination with the sugar and possibly also with a fruit acid under consideration according to the invention are used in the form of at least one extract of fruit and/or vegetables. Such an extract may especially be obtained by extraction of a ground material of fruit and/or vegetables with a solvent medium suitable for the extraction of the sugars, polyphenols andpossibly fruit acids contained in this ground material, this extraction being performed under reaction conditions, for instance of temperature and stirring, that are suitable for the extraction and that are suitable for the inactivation of polyphenol oxidase. The extract obtained after this extraction is directly usable in its native form, with the proviso that polyphenol oxidase, if present, is present in a form lacking in enzymatic activity. For the purposes of the present invention, the expression "free of polyphenol oxidase" means that the composition does not contain this enzyme in an active form. If it is naturally present in the extract of fruit or vegetables, source of polyphenol and sugar and possibly fruit acid, this extract undergoes a treatment, generally a heat treatment, intended to inactivate it, which generally leads to its degradation.

Thus, preferably, the process according to the invention consists in applying to keratin materials a composition that is free of polyphenol oxidase and that is totally or partly formed from at least one extract of fruit or vegetables simultaneously comprising at least one polyphenol in combination with at least one sugar and possibly also one fruit acid.

As examples of fruit and vegetables that may be used according to the invention, mention may be made especially of apple, lychee, apricot, grape, persimmon, pear, banana, avocado, bean, blackcurrant, blueberry, blackberry, cherry, cranberry, redcurrant, elderberry, grapefruit, kiwi, lentil, bilberry, mango, cherry, ginger, nectarine, onion, orange, kale, artichoke, asparagus, red cabbage, chive, aubergine, garlic, potato, parsley, peach, plum, radish, quince, suede, spinach, strawberry, mandarin, tomato, beetroot, broccoli, carrot, cauliflower, celery, guava, sweet potato, raspberry, medlar, papaya, pomegranate, pea, rice, kumquat, passion fruit, prickly pear (Opuntia cactus),

Indian gooseberry, buddha's hand, yuzu, citron, mikan, limequat, lemon and mexicani, and mixtures thereof.

Needless to say, these fruit and vegetables, which are particularly advantageous for their overall content of polyphenol, sugars and possibly also of fruit acid, may, on the other hand, distinguish themselves from each other significantly, via their specific content of one or other of these active agents.

Consequently, one fruit or vegetable may more particularly be selected over the others with regard to its high content of one of the compounds. Similarly, a composition according to the invention may use a mixture of extracts of fruit or vegetables, one of the extracts being most particularly advantageous for its high content of polyphenol and the other for its high content of sugar, and possibly with a third extract being particularly advantageous for its high content of fruit acid.

These choices fall within the competence of a person skilled in the art.

As regards the fruit rich in polyphenols and sugars, avocado, tomato, apple, banana, blackberry, blueberry, redcurrant, grape, kiwi, mango, orange, peach, pear, plum, raspberry and strawberry prove to be most particularly advantageous.

Even more preferentially, apple, pear, tomato and persimmon will be used. As vegetables that are rich in polyphenols and sugars, artichoke, asparagus, broccoli, red cabbage, carrot, cauliflower, celery, chive, aubergine, garlic, onion, kale, potato, radish and spinach are most particularly suitable for use in the invention.

Onion and garlic will preferentially be used. Apple, pear, persimmon, garlic and onion prove to be most particularly advantageous in terms of being a source of polyphenol and sugar in the context of the present invention.

As regards fruit, peach, medlar, cherry, blackcurrant, kumquat, papaya, tomato, avocado, passion fruit, apple, pear, persimmon, prickly pear (Opuntia cactus), Indian gooseberry, buddha's hand, yuzu, citron, mikan, limequat, lemon and mexicani, and mixtures thereof, may be mentioned with regard to their overall content of polyphenol and/or fruit acid.

Even more preferentially, apple, pear, blackcurrant, persimmon, prickly pear, Indian gooseberry, cherry, kumquat, avocado and passion fruit, and more particularly apple, will be used.

As vegetables, artichoke, asparagus, broccoli, red cabbage, carrot, cauliflower, celery, chive, aubergine, garlic, onion, kale, potato, radish and spinach are most particularly suitable for use in the invention with regard to their overall content of polyphenol and/or fruit acid. Onion and garlic will preferentially be used. Apple, pear, persimmon, garlic, broccoli and onion prove to be most particularly advantageous in terms of being a source of polyphenol and fruit acid in the context of the present invention.

According to one preferred embodiment, the fruit is (are) chosen from the fruit of plants of the Rosacea family, in particular of the genus Malus. According to one preferred embodiment, the fruit is chosen from apples chosen from Reinette de Cannes, Rambour d'Allemagne, Idared, Fuji, Fiorina, H. Dumont, Querina, Pomme de Bucey, Croque, Calville Rouge d'Ete, Nationale, Reinette d'Orleans, Nouvelle France, quince apple, Colapuy, Akane, Rambour d'Ete, Charden, Reinette Doree de Versailles, Rambour d'Hiver, Pommate d'Ervy, Reinette pepin, Baumann, Gala, Pomme Cloche, Estival, Jersey Mac, The Senator, Summered, Reinette Canada grey Bio, Calville du Roi, Benedictin, Judeline, Winter Banana, CuI d'Oison, Chataignier, Melrose, Api Etoile, Pomme Fraise, Avrolles, Limousine, Signe Tillish, Grand Alexandre, Pomme Raisin, Reinette Clochard, Doux Amer, Citron d'Hiver, Teint Frais, Cusset, Reinette d'Armorique, Reinette Franche, Antoinette, Genereuse de Vitry, Api Double, Archram and Kidds orange, and mixtures thereof, and/or from pears chosen from Doyenne du Cornice, Bergamote Crassane, Certeau d'Automne, Beurre Bachelier, Saint-Gilles, Colmar, Rateau, Beurre Clairgeau and Le Lectier, Carisi, saussinet gris, petite grise, brie pear, Royale d'hiver, Sucree de Montlucon, Gros Noir, Petit Noir, Callouat, Catillac, Saint Lezin, Imperiale a feuilles de chene, Bergamotte de Parthenay, sage pear and Charles Cognee, and mixtures thereof.

According to one particular embodiment, the polyphenol and sugar are used in the form of at least one extract of fruit or vegetables simultaneously comprising at least one polyphenol and at least one sugar.

According to an other particular embodiment, in the case the composition comprises also a fruit acid, the polyphenol, sugar and fruit acid are used in the form of at least one extract of fruit or vegetables simultaneously comprising at least one polyphenol, at least one sugar and at least one fruit acid.

According to another of its aspects, the present invention relates to a cosmetic composition of emulsion type containing, in a physiologically acceptable medium free of polyphenol oxidase, at least 5% by weight of a liquid fatty phase and at least one polyphenol in combination with at least one sugar and possibly also one fruit acid, the said polyphenol and the said sugar and possibly the said fruit acid being derived from fruit or vegetables.

According to one preferred variant, the polyphenol and the sugar are used in a (polyphenol(s)/sugar(s)) weight ratio and/or in respective amounts as defined below.

According to one preferred variant, in the case the composition comprises also a fruit acid, the polyphenol and the fruit acid are used in a fruit acid/polyphenol weight ratio and/or in respective amounts as defined below.

According to yet another of its aspects, the invention relates to a cosmetic assembly using a composition in accordance with the invention.

POLYPHENOLS

Polyphenols are structurally characterized by the presence of several phenolic groups associated in more or less complex structures generally of high molecular weight. They are water-soluble compounds, with a molecular weight of between 500 and 3000 daltons.

The polyphenol family is commonly subdivided into subfamilies, which are the tannins, lignins, flavonoids and anthocyans, which are all derived from the assembly of simple phenolic units.

The polyphenols that are found in large amount in fruit and vegetables are the flavonoids.

In the natural state, flavonoids are very often found in the form of heterosides; one or more of their phenol functions are then glycosylated, the saccharides being glucose, galactose, rhamnose or arabinose.

Flavonoids are divided into several classes that differ by the degree of saturation of the aglycone heterocycle, its oxidation and its spatial conformation. These are flavonols, anthocyanidins (or anthocyanidols) and flavonols, with the anthocyanidins possibly being obtained either via reduction of flavonols or via oxidation of flavonols.

Flavonols correspond to formula (I) below:

(I)

R3' |R5' H H Kaempferol

OH I ^H Quercetin

OH iOH Myricetin

OCH₃ I ^H Isorhamnetin Anthocyanidins have the following polyhydroxylated common structure (II):

(H)

As regards the flavan-3-ols, they have a polyhydroxylated common structure (III) as below:

(in) R H (+)-Catechin H (-)-Epicatechin

OH (+)-Gallocatechin OH (-)-Epigallocatechin

Furthermore, it should be noted that polyphenols are naturally present in fruit and vegetables in monomeric or polymeric forms. The monomeric forms are essentially catechin and epicatechin. Certain compounds are derived from these molecules via various substitutions; these are the procyanidols (epicatechin derivatives) and the prodelphinidols (gallocatechin or epigallocatechin derivatives). They are the precursors of condensed tannins. Mention may also be made, as monomers, of phloretin, phloridzin (phloretin 20-glucoside), caffeic acid, chlorogenic acid, coumaric acid, gallic acid and quercetin, and derivatives thereof.

The oligomeric or polymeric forms comprise, for their part, the procyanidins (catechin oligomers or polymers) and the prodelphinidins (gallocatechin oligomers or polymers).

According to one particular embodiment, the polyphenol under consideration according to the invention combines at least one polymeric form and at least one monomeric form of polyphenol.

For the purposes of the invention, the term "polyphenol" is used to denote, without preference, a single polyphenol derivative or a mixture of several polyphenol derivatives as defined above, whether they are, without preference, in monomeric or polymeric form. Generally, it denotes a mixture of polyphenols that are different from each other.

The composition in accordance with the invention advantageously has a polyphenol content of greater than or equal to 0.001%, in particular greater than or equal to 0.01% and especially greater than or equal to 0.05% expressed as gallic acid equivalent relative to the total weight of the said composition.

Similarly, a composition in accordance with the invention advantageously has a polyphenol content of less than or equal to 75% by weight and more advantageously less than or equal to 65% by weight expressed as gallic acid equivalent relative to the total weight of the said composition.

According to one particular mode, a composition in accordance with the invention has a polyphenol content of less than or equal to 50% by weight, preferably less than or equal to 30% by weight, more preferably less than or equal to 20% by weight, or even less than or equal to 10% by weight, expressed as gallic acid equivalent relative to the total weight of the said composition.

This quantification as total polyphenols, i.e. in polymeric and monomeric forms, is performed according to the Folin method, which is the method conventionally adopted for assaying phenolic compounds. This is a biochemical analytical method based on a spectrocolorimetric measurement.

The reagent is constituted of a mixture of phosphotungstic acid (H3PW12O40) and phosphomolybdic acid (H3PM012O40). It is reduced, during the oxidation of phenols, to a mixture of blue oxides of tungsten and of molybdenum (Ribereau-Gayon, 1968). The coloration produced, whose maximum absorption is between 725 and 750 nm, is proportional to the amount of polyphenols present in the analysed plant extracts. Reading of the absorbance at 735 nm is performed by means of a spectrophotometer. The mean polyphenol concentration is expressed in μg of gallic acid equivalent.ml^"1, for example, if gallic acid is chosen as control. Reagents suitable for this measurement are available in commercial form.

Illustrations of these that may especially be mentioned include the product sold by the company Isitec Lab and distributed by the company Seppal. The conditions for using this reagent are more particularly those outlined in the examples below.

As stated previously, the polyphenols under consideration according to the invention are mixtures of polymeric forms and of monomeric forms of polyphenols.

Naturally, these two forms are present in fruit and vegetables comprising polyphenols, but in very different concentration ratios depending on the variety of fruit or vegetable under consideration.

According to one particular mode of the invention, these two forms are present in a composition according to the invention in a (polymeric polyphenol(s)/monomeric polyphenol(s)) weight ratio of greater than or equal to 9, preferably greater than or equal to 11 and even more advantageously greater than or equal to 14. Quantification of this ratio may be obtained by performing, in parallel to the evaluation of the total polyphenols according to the Folin method outlined above, an assay by reverse-phase liquid chromatography of the monomeric forms present in these total polyphenols coupled to a UV detection method and using one phenolic standard per category of compound, generally gallic acid. This method is outlined in detail in the examples below.

The amount of total polyphenols assayed by the Folin method, expressed in gallic acid units Cζ°^_c and the amount of monomeric polyphenol assayed by HPLC-UV and also reported in gallic acid units C"^ make it possible to determine by subtraction the polymeric fraction of the polyphenols.

The ratio is then defined by the convention:

^ Folin _ f^HPLC

R = - Gallic ^Gallic y^ HPLC ^Gallic

According to one particular embodiment, the polyphenol in accordance with the invention contains less than 75% by weight, in particular less than 30% and better still less than 15% by weight of phloridzin, expressed as gallic acid equivalent, relative to the total weight of polyphenol, in the cosmetic composition.

As stated previously, the polyphenols are advantageously used in the context of the invention in the form of an extract of fruit and/or vegetables.

As examples of fruit and vegetables that may be used according to the invention, mention may be made especially of apple, lychee, apricot, grape, persimmon, pear, banana, avocado, bean, blackcurrant, blueberry, blackberry, cherry, cranberry, redcurrant, elderberry, grapefruit, kiwi, lentil, bilberry, mango, nectarine, onion, garlic, parsley, chive, ginger, orange, peach, plum, radish, quince, suede, spinach, strawberry, mandarin, potato, artichoke, asparagus, aubergine, raspberry, tomato, beetroot, broccoli, red cabbage, carrot, cauliflower, kale, celery, guava, sweet potato, medlar, papaya, pomegranate, pea and rice.

The polyphenols are particularly present in fruit such as apple, pear, grape and cherry, with about 500 mg of polyphenol/ 100 g of raw fruit, and persimmon with about 1 g of polyphenol/ 100 g of raw fruit. As vegetables that are particularly rich in polyphenol, mention may be made more particularly of onion, garlic, kale, broccoli, parsley and celery. Biorenewable sources that are particularly advantageous in terms of amount of polyphenols, sugars and also possibly of fruit acid advantageously belong to the Rosacea family, in particular of the genus Malus.

The Rosacea family includes more than two thousand species divided into over a hundred genera.

This cosmopolitan family of perennial herbaceous plants, shrubs or trees especially includes the subfamily Maloideae, to which belong the plants of the following genera: the genus Cydonia, whose fruit is the quince; the genus Fragaria, whose fruit is the strawberry; the genus Pyrus, whose fruit is the pear; the genus Mespilus, whose fruit is the medlar; the genus Prunus, whose fruit are the raspberry and the blackberry; and the genus Malus, whose fruit is the apple.

Varieties of pear that may especially be mentioned include the varieties Bergamot, Beurre, Conference, Doyenne, Fondante, President, Carisi, De Brie, De Sauge, Saussinet Gris and Triomphe. Varieties of strawberry that may especially be mentioned include the varieties

Ambrosia, Capron royal, Jucunda, Marlate, Perle de Prague and Souveraine.

Varieties of cherry that may especially be mentioned include the varieties Burlat, Cceur de pigeon, Montmorency, Napoleon, Noir d'Ecully and Bigarreau.

Varieties of peach that may especially be mentioned include Amsden peach, Charles Ingouf peach, grosse mignonne peach, Mayflower peach, vine peach, Red Haven peach, Savoie blood peach and vine blood peach.

Varieties of raspberry that may especially be mentioned include the varieties faro, gradina, sweet Lulu, Sauron red, Anna F, Carmen love, heritage, Joan squire, Ruby and Purple royalty. According to one preferred embodiment variant, the polyphenols are used in the form of an apple extract. Apple trees form part of the genus Malus, which includes about 40 species of trees and shrubs, the most important of which is the common apple tree or Malus pumila which includes varieties of cider apples and varieties of dessert apples.

Apples that have reached a sufficient degree of ripeness, i.e. compatible with consumption either in the form of fruit (dessert apples) or drink (cider apples) are most particularly suitable for use in the invention. These apples have an enriched polyphenol content compared with apples of a lesser degree of ripeness. As apples that are suitable for use in the invention, mention may be made of: Reinette Grise de Saintonge, Nez Plat, Transparente Blanche, Api Noir, Saulette, Fenouillet Gris Anise, Orange apple, Initial, Idared, Fuji, Fiorina, Grillot, Calville St Sauveur, Charge Bas, Pomme Pinon, Pomme de Glace, Astrakan Blanc, Pomme des Moissons, Astrakan Rouge, Calville Blanc d'Hiver, Patte de Loup, Transparente de Croncels, Belle Fille des Salins, Reinette du Mans, Framboise d'Oberland, English Reinette, Cardinal, Sauvageon Barre, Anna, Belle fleur jaune, fig apple, Museau de Lievre, Petit Bon, Gros Locart Vert, banana apple, Borowitsky, Elisa Raetke, Canada grey Reinette, Henri Dumont, Golden Royale, Reinette Grand-mere, Cabassou, Reinette Martin, Rambour Papeleu, Belle de Pontoise, Court Pendu Gris, Reinette de Caux, Jean Lefevre, Pomme de Verite, Barbarie, Reinette Grise de Vitry, Rouge de Treves, Glenon, Durette, Nouvelle Europe, Reinette du Vigan, Francatu, Cramoisie de Croncels, Gravenstein, San Jacinto, Court Pendu Rouge, Pomme de l'Estre, Reinette des Cannes, Rambour d'Allemagne, Querina, pomme de Bucey (or Pommate de Bucey), Croque, Calville Rouge d'Ete, Nationale, Reinette d'Orleans, Nouvelle France, Pomme Coing, Colapuy, Akane, Rambour d'ete, Charden, Reinette Doree de Versailles, Rambour d'Hiver, Pommate d'Ervy, Reinette Baumann, Gala, Pomme Cloche, Estival, Jersey Mac, The Senator, Summered, Canada grey Reinette Bio, Calville du Roi, Benedictin, Judeline, Winter Banana, CuI d'Oison, Chataignier, Melrose, Api Etoile, strawberry apple, Avrolles, Limousine, Signe Tillish, Grand Alexandre, grape apple, Reinette Clochard, Doux Amer, Citron d'Hiver, Teint Frais, Cusset, Reinette d'Armorique, Reinette Franche, Antoinette, Genereuse de Vitry, Api Double, Archram and Kidds Orange (or Kid Orange Red).

The variety is preferably Reinette de Cannes, Rambour d'Allemagne, Idared, Fuji, Fiorina, Querina, Pomme de Bucey, Croque, Calville Rouge d'Ete, Nationale, Reinette d'Orleans, Nouvelle France, quince apple, Colapuy, Akane, Rambour d'Ete, Charden, Reinette Doree de Versailles, Rambour d'Hiver, Pommate d'Ervy, Reinette pepin Baumann, Gala, Pomme Cloche, Estival, Jersey Mac, The Senator, Summered, Canada grey Reinette Bio, Calville du Roi, Benedictin, Judeline, Winter Banana, CuI d'Oison, Chataignier, Melrose, Api Etoile, strawberry apple, Avrolles, Limousine, Signe Tillish, Grand Alexandre, grape apple, Reinette Clochard, Doux Amer, Citron d'Hiver, Teint Frais, Cusset, Reinette d'Armorique, Reinette Franche, Antoinette, Genereuse de Vitry, Api Double, Archram and Kidds orange or Kid Orange Red. According to one particular mode of the invention, the apples selected as the source of polyphenol(s) having a (polymeric polyphenol(s)/monomeric polyphenol(s)) weight ratio of greater than or equal to 9 are the varieties Fiorina, Reinette d'Orleans,

Nouvelle France, quince apple, Colapuy, Akane, Rambour d'ete, Reinette Doree de Versailles, Rambour d'Hiver, Pommate d'Ervy, Reinette Baumann, Gala, Pomme Cloche,

Estival, Jersey Mac, The Senator, Summered, Canada grey Reinette Bio, Calville du Roi,

Benedictin, Judeline, Winter Banana, CuI d'Oison, Chataignier, Melrose, Api Etoile, strawberry apple, Avrolles, Limousine, Signe Tillish, Grand Alexandre, grape apple,

Reinette Clochard, Doux Amer, Citron d'Hiver, Teint Frais, Cusset, Reinette d'Armorique, Api Double, Archram and Kidds Orange (or Kid Orange Red).

They are preferably dessert apples.

According to one preferred mode, the variety Idared is used.

According to another preferred mode, the variety Fuji is used.

According to another preferred mode, the variety Fiorina is used. According to yet another preferred mode, the variety Estival is used.

The preparation of the fruit and/or vegetable extracts that are suitable for use in the invention proceeds according to conventional techniques and generally involve a step of pressing followed by a step of extraction especially as described in the document EP 0 657 169. The extraction methods clearly fall within the competence of a person skilled in the art. In general, they use an extraction solvent that is, of course, chosen for its ability to extract the polyphenols, sugars and possibly also fruit acids contained in the fruit or vegetables under consideration.

This extraction solvent may be a polar solvent, in particular an aqueous or aqueous-alcoholic solvent formed by mixing water with at least one solvent such as methanol or ethanol. Examples of such extraction methods are described in "Flavan and proanthocyanidins" L.J. Porter in "The flavonoids" eds J.B. Harborne 1988 Chapman &

Hall Ltd. ISBN 0-412-28770-6.

The type of extraction will be adapted to the starting raw material. Usually, the types of solvent used are: alcoholic solvent (methanol or ethanol) or aqueous-alcoholic solvent (methano I/water (50/50) or ethanol/water (50/50)).

The extract may be obtained by extracting the whole fruit or vegetable or selective extraction of at least one of its components such as the skin, the pulp, the seeds and mixtures thereof. Advantageously, the extract is derived from extraction of the whole fruit.

During the preparation of the extract, advantageously after the extraction, the extract under consideration according to the invention may undergo an additional treatment intended to inactivate the enzymes naturally present in the fruit or vegetable, in particular polyphenol oxidase, which is responsible for the browning naturally observed on the flesh of a fruit or vegetable in contact with the air. One solution consists in cooking or pasteurizing the extract at the end of the extraction, heat having the effect of breaking the molecular bonds that give the enzymes their form. A short exposure to temperatures of 70 to 90⁰C generally suffices to deactivate the enzymes. Another solution consists in lowering the pH of the extract.

The extract, source of polyphenol, or the composition in accordance with the invention may also be characterized in terms of antioxidant activity, especially according to the ORAC method (abbreviation for Oxygen Radical Absorbance Capacity). This method is based on the capacity of antioxidants to inhibit the degradation of a model substrate, fluorescein, induced by a radical initiator, AAHP (2,2'-azobis(2- amidinopropane) dihydrochloride).

The degradation of the fluorescein is monitored by measuring the decrease in the native fluorescence. Such a test is described in greater detail in the examples below. According to one particular mode, the ORAC antioxidant activity of the extract in accordance with the invention is greater than 4 μmol of Trolox equivalent per g of extract, and the ORAC antioxidant activity of the composition according to the invention is greater than 0.1 μmol of equivalent/g of composition.

The fruit and vegetables whose total antioxidant capacity is particularly large are especially apple, grape, cherry, persimmon, artichoke, asparagus, avocado, blackberry, blueberry, broccoli, red cabbage, chive, cranberry, garlic, ginger, redcurrant, mango, onion, orange, peach, pear, plum, potato, radish, raspberry, spinach, strawberry and tomato.

SUGARS As stated previously, the polyphenols are used in the context of the present invention in combination with at least one sugar. The sugar(s) as defined hereinbelow may or may not be present in the extract containing the polyphenols.

Preferably, the sugar(s) as defined below are present in the same fruit or vegetable extract containing the polyphenols. Preferably, the polyphenols and/or the sugars used in the context of the present invention are derived from apples and/or pears.

According to one variant, the polyphenols and sugars may also originate from several different sources, in order in particular to be able to compensate for the deficit of one of the polyphenol or sugar compounds in a fruit or vegetable, via another fruit or vegetable that is rich in this compound.

Sugars or carbohydrates are conventionally separated into two categories depending on their size. Simple sugars (small molecules composed of one or two carbohydrate units) and complex sugars (long chains composed of several carbohydrate units) are thus distinguished. By way of illustration, the simple sugars are glucose, sucrose, fructose and sorbitol.

As representative of the complex sugars, mention may be made especially of starch.

For the purposes of the invention, the term "sugar" covers, without preference, a single sugar or a mixture of sugars, whether they are, without preference, simple or complex.

As stated previously, the sugars are also derived from fruit or vegetables in the context of the present invention. Preferably, the sugars are used in the context of the present invention in the form of a fruit and/or vegetable extract. Simple or complex sugars are naturally present in the majority of fruit and vegetables. Among these, fruit and vegetables such as garlic, banana, potato, grape, persimmon, cherry, mango, apple, pear, plum, blackberry, lychee, apricot, kiwi, blueberry, ginger, bean, orange, peach, red beetroot, artichoke, onion, strawberry, carrot, quince, raspberry, redcurrant, aubergine, cauliflower, asparagus, radish and tomato prove to be most particularly rich in sugars.

According to one particular mode, the composition in accordance with the invention contains at least one simple sugar derived from fruit or vegetables. Preferably, the composition in accordance with the invention contains at least one simple sugar and at least one complex sugar derived from fruit or vegetables.

Preferably, the sources rich in simple sugars are apple, pear, persimmon and apricot, and the sources rich in complex sugars are pea, garlic, potato and tomato. As stated previously, it is possible to demonstrate the presence of sugar in a composition in accordance with the present invention according to the acid hydrolysis method. This method may consist in characterizing the formation of 5- (hydroxymethyl)furfural produced by acid hydrolysis of the sugar.

These sugars may also be quantified in the extract via conventional methods, for instance high-performance ionic chromatography coupled to amperometric detection, and more particularly the method described in the examples given hereinbelow, which allows glucose, fructose, lactose and sucrose to be simultaneously assayed.

As stated previously, the polyphenol and sugar combination is advantageously used in the context of the present invention in a (polypheno I/sugar) weight ratio of less than or equal to 3, in particular less than or equal to 1 and in particular less than or equal to 0.5.

Thus, according to one advantageous embodiment, the sugar is present at more than 50% by weight and advantageously from 60% to 75% by weight relative to the total weight of sugar and polyphenol. In particular, a composition according to the invention may comprise a sugar content of greater than or equal to 6%, better still greater than or equal to 8%, even more advantageously greater than or equal to 12% and particularly greater than or equal to 15% relative to its total weight.

FRUIT ACIDS

As stated previously, a composition according to the invention may comprise besides the association of at least one polyphenol with at least one sugar, at least one fruit acid.

The fruit acid(s) as defined hereinbelow may or may not be present in the extract containing the polyphenols and possibly also the sugars.

Preferably, the fruit acid(s) as defined hereinbelow is (are) present in the same fruit or vegetable extract containing the polyphenols and possibly also the sugars. As examples of fruit and vegetables that are particularly rich in fruit acid and in polyphenol, mention may be made of apple, pear, blackcurrant, kumquat, persimmon, kaffir lime, yuzu, limequat, lemon, mexicani, pomegranate, peach, cherry, medlar, avocado, Indian gooseberry, broccoli and passion fruit. Preferably, the polyphenols and/or fruit acids used in the context of the present invention are obtained from apples.

According to one variant, the polyphenols, sugars and fruit acids may also be derived from several different sources, in order in particular to be able to compensate for the deficiency of one of the polyphenol, sugar or fruit acid compounds in a fruit or vegetable, via another fruit or vegetable that is rich in this compound.

For the purposes of the invention, the term "fruit acid" denotes any acidic compound naturally present in a fruit.

They are more particularly hydroxy acids, in particular α-hydroxy acids, and more particularly in the L form. Representatives of these acids that may especially be mentioned include L- tartaric acid, malic acid, quinic acid, shikimic acid, citric acid, succinic acid, fumaric acid, lactic acid, suberic acid, gly colic acid, glutaric acid, acetic acid and malonic acid.

Preferably, it is malic acid, in particular L-malic acid.

Among the fruit and vegetables rich in malic acid, mention may be made of peach, medlar, cherry, blackcurrant, kumquat, papaya, tomato, pomegranate, broccoli, Indian gooseberry, persimmon, kaffir lime, yuzu, mexicani, limequat, lemon, avocado, passion fruit, apple and pear.

Among the varieties of apples that are rich in malic acid, mention may be made in particular of Idared, Fiorina, Fuji and Estival, and among the pears that are rich in fruit acid, mention may be made of Doyenne du Commice, Bergamote Crassane, Certeau d'Automne, Beurre Bachelier, Saint-Gilles, Colmar, Rateau, Beurre Clergeau, Le Lectier,

Carisi, Saussinet Gris, Petite Grise, poire De Brie, poire De sauge and Virgouleuse.

According to one preferred embodiment variant, the fruit acid is used in the form of an apple extract. For the purposes of the invention, the term "fruit acid" is used to denote, without preference, a single fruit acid or a mixture of several fruit acids as defined above. It is possible to quantify the fruit acid content in the extract via conventional methods, for instance high-performance liquid chromatography by exclusion coupled to a UV diode array detector, as described in the examples given below.

Malic acid, which is the fruit acid predominantly present in fruit and vegetables, may also be specifically quantified in the extract via an enzymatic method, as described in the examples below, using a characterization by visible spectrophotometry, first involving an enzymatic oxidation of the L-malic acid with L-malate dehydrogenase.

According to one particular embodiment, the fruit acid is present in a composition of the invention in an amount of greater than or equal to 0.05% by weight, in particular ranging from 0.07% to 20% and more particularly from 0.1% to 10% by weight relative to the total weight of the said composition.

According to yet another particular embodiment, thepolyphenols and the fruit acids are advantageously used in the context of the present invention in a fruit acid/polyphenol weight ratio of greater than or equal to 0.02, advantageously greater than or equal to 0.3, even more advantageously greater than 0.4 and better still greater than or equal to 1.

Moreover, the fruit and/or vegetables such as those mentioned previously naturally contain vitamins, which it may also be advantageous to exploit with the polyphenols, sugars and possibly also with the fruit acids.

Thus, another embodiment may consist in using, in a composition intended for a cosmetic process for treating keratin materials, at least one polyphenol in combination with at least one vitamin, both being derived from fruit and/or vegetables.

Generally, vitamins are separated into two groups: water-soluble vitamins and liposoluble vitamins.

Representatives of water-soluble vitamins that may be mentioned include vitamin Bl (thiamine), vitamin B2 (riboflavin), vitamin B3 (nicotinamide), vitamin B5 (pantothenic acid), vitamin B6 (pyridoxine), vitamin B8 (biotin), vitamin B9 (folic acid), vitamin B 12 (cobalamin), vitamin C (ascorbic acid) and vitamin H. As regards the liposoluble vitamins, they may be vitamin A (retinol), vitamin D

(calcipherol), vitamin E (tocopherol), vitamin Kl (phylloquinone) and vitamin K2 (menaquinone). As examples of fruit and vegetables that are particularly rich in vitamin A, mention may be made especially of apricot, beet, nectarine, Swiss chard, chicory, courgette, spinach, lettuce, lamb's lettuce, mange-tout, sorrel, parsley and dandelion.

As examples of fruit and vegetables that are particularly rich in vitamin Bl, mention may be made especially of banana, chicory, cabbage, Brussel sprout, cauliflower, cress, date, spinach, dried bean, lettuce, lentil, lamb's lettuce, mange-tout, hazelnut, walnut, orange, sorrel, grapefruit, and dandelion, fresh pea, dried pea, prune, radish, escarole and soybean.

As examples of fruit and vegetables that are particularly rich in vitamin B2, mention may be made especially of aubergine, beet, hazelnut, walnut, prune and soybean.

As examples of fruit and vegetables that are particularly rich in vitamin C, mention may be made especially of garlic, asparagus, aubergine, beet, Swiss chard, blackcurrant, green celery, chicory, cabbage, Brussel sprout, cauliflower, lemon, cress, spinach, strawberry, raspberry, currant, gooseberry, lettuce, lamb's lettuce, mandarin, mange-tout, blackcurrant, turnip, hazelnut, walnut, onion, orange, sorrel, grapefruit, parsley, dandelion, leek, fresh pea, radish, rhubarb, suede, broccoli, apple, pear, blackcurrant, prickly pear and persimmon.

Among the fruit and vegetables that prove to be rich in D vitamins, mention may be made of nectarine and coconut. Among the fruit and vegetables that prove to be rich in E vitamins, mention may be made of almond, nectarine, cress, green bean, dried bean, lettuce, lentil, mange- tout, hazelnut, walnut, fresh pea and dried pea.

As stated previously, the compositions according to the invention are cosmetic or dermatological compositions. They are preferably cosmetic compositions. The compositions according to the invention find their application in a large number of treatments, especially cosmetic treatments for the skin, including the scalp, the hair, the nails and/or mucous membranes, in particular for caring for, cleansing and/or making up and/or sun-protecting the skin and/or mucous membranes.

The compositions according to the invention may be cosmetic makeup compositions of the type such as foundations, makeup rouge, eyeshadow, concealer products or blusher, or alternatively a body makeup product or skin colouring product or cosmetic care and/or cleansing compositions especially for the skin, for instance a composition for protecting, treating or caring for the face or the body.

Examples that may be mentioned include day creams, night creams, makeup- removing creams, antisun compositions, protective or care body milks, after-sun milks, skincare lotions, gels or mousses, artificial tanning compositions and aftershave compositions.

The compositions according to the invention comprise a physiologically acceptable medium, i.e. a non-toxic medium that can be applied to human keratin materials, which is of pleasant appearance, odour and feel. They may be in any galenical form conventionally used for topical application and especially in the form of aqueous or aqueous-alcoholic solutions, oil-in-water (O/W) emulsions, water-in-oil (W/O) emulsions or multiple emulsions (triple: W/O/W or 0/W/O), aqueous gels, or dispersions of a fatty phase in an aqueous phase using polymer particles such as spheres and capsules, or lipid vesicles of ionic and/or nonionic type (liposomes, niosomes or oleosomes), emulsions, or thin films.

More particularly, it is a composition of emulsion type containing at least 5% by weight, in particular at least 10% by weight or even advantageously from 15% to 60% by weight and especially from 20% to 50% by weight of a liquid fatty phase.

The fatty or oily phase, when it is present, may contain oils, pasty fatty substances, waxes, silicone resins or silicone elastomers, and mixtures thereof.

The oils may be volatile or non- volatile and may be, for example, hydrocarbon- based oils especially of animal, mineral or plant origin, synthetic oils, silicone oils or fluoro oils, or mixtures thereof.

The aqueous phase may comprise water and/or at least one water-miscible organic solvent (miscibility in water of greater than 50% by weight at 25°C), for instance lower monoalcohols containing from 1 to 5 carbon atoms.

The compositions according to the invention may also contain at least one adjuvant chosen from cosmetic or dermatological active agents, preserving agents, hydrophilic or lipophilic gelling agents, nonionic, anionic or cationic surfactants, antioxidants, salts, fragrances, fillers, pigments, UV-screening agents, odour absorbers and dyestuffs, and mixtures thereof. The cosmetic or dermato logical active agent may be chosen especially from moisturizers, desquamating agents, agents for improving the barrier function, depigmenting agents, antioxidants, dermo-decontracting agents, anti-glycation agents, agents for stimulating the synthesis of dermal and/or epidermal macromolecules and/or for preventing their degradation, agents for stimulating fibroblast or keratinocyte proliferation and/or keratinocyte differentiation, agents for promoting the maturation of the horny envelope, NO-synthase inhibitors, peripheral benzodiazepine receptor (PBR) antagonists, agents for increasing the activity of the sebaceous glands, agents for stimulating the energy metabolism of cells, tensioning agents, lipo -restructuring agents, slimming agents, agents for promoting the cutaneous capillary circulation, calmatives and/or anti- irritants, sebo- regulators or anti-seborrhoeic agents, astringents, cicatrizing agents, anti-inflammatory agents and antiacne agents, and mixtures thereof.

Natural adjuvants, in particular natural cosmetic or dermatological active agents, even more advantageously biorenewable adjuvants and in particular biorenewable active agents, are particularly preferred.

The amounts of these various ingredients are those conventionally used in the fields under consideration, for example from 0.01% to 20% by weight relative to the total weight of the cosmetic or dermatological composition and from 0.1% to 10% by weight relative to the total weight of the said composition. Needless to say, a person skilled in the art will take care to select the optional additional additives and/or the amount thereof such that the advantageous properties of the combination of the polyphenol with at least one sugar and possibly also with one fruit acid under consideration according to the invention are not, or are not substantially, adversely affected by the envisaged addition.

Cosmetic assembly

According to another aspect, the invention also relates to a cosmetic assembly comprising:

(i) at least one container delimiting at least one compartment, the said container being closed by a closing member; and

(ii) at least one composition placed inside the said compartment and as defined previously. The container may be in any suitable form. It may especially be in the form of a bottle, a tube, ajar, a case, a can, a sachet or a box.

The closing member may be in the form of a removable stopper, a lid, a cover, a tear-off strip or a cap, especially of the type comprising a body fixed to the container and a cap articulated on the body. It may also be in the form of a member ensuring the selective closure of the container, especially a pump, a valve or a clapper.

The container may be combined with an applicator. The applicator may be in the form of a fine brush, as described, for example, in patent FR 2 722 380. The applicator may be in the form of a block of foam or of elastomer, a felt or a spatula. The applicator may be free (tuft or sponge) or securely fastened to a rod borne by the closing member, as described, for example, in patent US 5 492 426. The applicator may be securely fastened to the container, as described, for example, in patent FR 2 761 959.

The composition according to the invention may be contained directly in the container, or indirectly. By way of example, the composition may be arranged on an impregnated support, especially in the form of a wipe or a pad, and arranged (individually or in plurality) in a box or in a sachet. Such a support incorporating the product is described, for example, in patent application WO 01/03538.

The closing member may be coupled to the container by screwing.

Alternatively, the coupling between the closing member and the container is done other than by screwing, especially via a bayonet mechanism, by click-fastening, gripping, welding, bonding or by magnetic attraction. The term "click- fastening" in particular means any system involving the crossing of a bead or cord of material by elastic deformation of a portion, especially of the closing member, followed by return to the elastically unconstrained position of the said portion after the crossing of the bead or cord. The container may be at least partially made of thermoplastic material.

Examples of thermoplastic materials that may be mentioned include polypropylene or polyethylene.

Alternatively, the container is made of non-thermoplastic material, especially glass or metal (or alloy). The container may have rigid walls or deformable walls, especially in the form of a tube or a tubular bottle. The container may comprise means for initiating or facilitating the distribution of the composition. By way of example, the container may have deformable walls so as to allow the composition to exit in response to a positive pressure inside the container, this positive pressure being caused by elastic (or non-elastic) squeezing of the walls of the container.

The container may consist of a carton with a base delimiting at least one housing containing the composition, and a lid, especially articulated on the base, and capable of at least partially covering the said base. Such a carton is described, for example, in patent application WO 03/018423 or in patent FR 2 791 042. The container may be equipped with a drainer arranged in the region of the aperture of the container. Such a drainer makes it possible to wipe the applicator and possibly the rod to which it may be securely fastened. Such a drainer is described, for example, in patent FR 2 792 618.

According to one particular mode of the invention, the assembly may comprise:

- a composition A according to the invention,

- a composition B, conditioned separately from composition A, comprising at least one additional cosmetic or dermatological active agent.

In this case, compositions A and B may be conditioned separately in two compartments, formed either by two separate containers, or in a single device.

In particular, the said polyphenol, the said sugar and possibly also the fruit acid are present in the said composition A in the form of a single crude extract of fruit or vegetable naturally containing them.

The term "single device" means a device via which the two compartments are integrally attached to each other. Such a device may be obtained via a process of moulding two compartments as a single component, especially made of a thermoplastic material. It may also result from any form of assembling, especially by bonding, welding or other click- fastening.

According to a first embodiment, the two containers are independent of each other. Such containers may be in various forms. They may especially be tubes, bottles or drums. One and/or the other of the containers may be mounted with a manually- actuated pump on which is mounted a push-button for actuating the pump and dispensing the composition via at least one dispensing orifice.

Alternatively, one and/or the other of the containers is pressurized, especially by means of a propellant, in particular a propellant gas. In this case, the container(s) is (are) equipped with a valve on which is mounted a push-button equipped with a nozzle or any other diffusion means for dispensing the product.

The propellant may be in a mixture with the composition to be dispensed or separated, especially via a piston that can slide inside the container, or via the flexible walls of a bag inside which the composition is placed.

The containers may be made of various materials: plastic, glass or metal.

Alternatively also, the two compartments are formed from two concentric compartments formed inside a tube, and mounted thereon is a pump with no air reuptake, and equipped with a push-button with one or two dispensing orifices. Provided inside the tube is a piston that rises in the direction of the pump as and when the compositions are withdrawn from inside the containers. Such dispensing modes are especially used for dispensing toothpastes.

The invention will now be illustrated.

EXAMPLE 1:

1.1. Protocol for extracting fruit and vegetables

For each variety of fruit and vegetables, an appropriate specimen mass of the whole fruit or vegetable in the form of quarters is ground so as to form a paste, which is then mixed homogeneously with Fontainebleau sand, and the samples obtained are then successively introduced into an ASE 200® extractor sold by the company Dionex.

The ASE 200® is an automated system for extracting organic compounds, which accelerates the traditional extraction processes. The extraction solvent used is an

MeOH/water mixture (70/30). The extraction takes place at 60⁰C with 15 ml of the said

MeOH/water mixture, at a pressure of 1000 psi applied to the extraction cell containing the sample, to maintain the heated solvent in liquid form. The operation is repeated three times. At the end of the extraction, a volume of 45 ml of fruit or vegetable extract and of extraction solvent is recovered, ready for analysis.

For example, 5 g of ground raw apple of each of the varieties Idared, Fuji and Fiorina are used to prepare, according to this protocol, extracts of each variety of apple.

The same protocol is used to prepare the fruit and vegetable extracts listed in Table 5 presented hereinbelow.

The following assays and characterizations were performed on the fruit or vegetable extracts thus obtained.

1.2 Protocol for determining the polyphenol, L-malic acid and sugar contents of the fruit and vegetable extracts 1.2.1. Polyphenol content of the fruit and vegetable extracts

i) Assay on the total polyphenols of each extract via the Folin-Ciocalteu colorimetric method

Determination of the content of total polyphenols in the extracts prepared as described previously was performed via the Folin-Ciocalteu colorimetric method.

This method makes it possible to perform the assay of total polyphenols, i.e. in polymeric and monomeric form, via visible spectrometry at 620 nm using the Folin- Ciocalteu reagent (Ref. 9001, Merck). This reagent is constituted of a mixture of phosphotungstic acid and phosphomolybdic acid, which is reduced during the oxidation of phenols to a mixture of blue oxides of tungsten and of molybdenum. The intensity of the colour developed is proportional to the content of phenol in the compounds present in the analysed extract.

The results of the assay of the contents of total polyphenols in each fruit or vegetable extract are given in Table 5 below. The values therein are given as mass percentages of gallic acid equivalent per gram of analysed extract using gallic acid as standard. U) Assay of the monomeric polyphenols of each extract via liquid chromatography coupled to a UV-visible diode array detector

Assay of the main constituent monomeric polyphenols of each extract is performed by reverse-phase liquid chromatography on an ACE C 18 HL, sold by ATI, coupled to a UV-visible diode array detector between 250 and 400 nm.

The identification and quantification were performed on the fruit or vegetable extracts described previously, by external calibration, the standards being phloridzin and chlorogenic acid. The assayed polyphenols are chlorogenic acid, phloridzin, phloretin, catechin, epicatechin, epigallocatechin, fumaric acid, quercetin and the glycosyl derivatives thereof.

Table 1 below reports, by way of example, the results obtained via this assay for three varieties of apple.

TABLE 1

i) Characterization of the (polymeric polyphenols/monomeric polyphenols) ratio for each extract

As stated previously, quantification of this ratio may be obtained by performing, in parallel to the evaluation of the total polyphenols according to the Folin method outlined above, an assay by reverse-phase liquid chromatography of the monomeric forms present in these total polyphenols coupled to a UV detection method using one phenolic standard per category of compound, generally gallic acid.

This characterization is detailed below for the Idared apple variety.

First, the following relationships are established between gallic acid and the monomeric polyphenols in the assay of the total polyphenols:

Chlorogenic acid x 0.69 = Gallic acid Phloridzin x 0.49 = Gallic acid

Quercetin x 0.93 = Gallic acid.

On the basis of these relationships, the contents of chlorogenic acid, phloridzin and quercetin given in Table 1 are converted into gallic acid for the Idared variety. The following is thus obtained:

C_G^ = [l80x0.69 + 60.8x0.49 + 15.3x0.93]^_{g /g}x0.0001 C"_a ^Pm_c = 0.0169%

The ratio R is deduced therefrom, which is given by the following relationship: fiFohn _ (iHPLC

R = -¹ GaUiC -¹GaUiC

C HPLC Gallic

In the case of the Idared variety, the value from Table 5 of

C_GJ° _ι"_c = 0.099 % is reported therein for the total polyphenol concentration. This gives:

0.099% - 0.0169% 0.0169%

As examples of results, the values of R obtained for three varieties of apple are given in Table 2 below.

TABLE 2

H) Characterization of the antioxidant activity of the polyphenols of each extract via the ORAC method (abbreviation for "Oxygen Radical Absorbance Capacity") This method measures the oxidative degradation of the fluorescent molecule, fluorescein, after it has been mixed with free-radical initiators, such as AAPH or 2,2'- azobis(2-amidinopropane) dichloride, which will produce peroxyl free radicals by heating, which damages the fluorescein molecule. The polyphenols, which are antioxidants, protect the fluorescein molecule against oxidative decomposition. The degree of protection is quantified using a fluorimeter sold under the name Thermoelectron Corporation

Fluoroskan Ascent FL. The degree of antioxidant protection is assessed using Trolox® (6- hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid) as reference antioxidant, the cyclic molecular structure of which is similar to that of vitamin E. Various concentrations of

Trolox® are used to obtain a reference curve. The curves produced with the samples are then compared with this curve.

By way of example, the results obtained for three analysed apple extracts are collated in Table 3 below.

TABLE 3

*determined via the Folin method

1.2.2. Sugar content of the fruit and vegetable extracts i) Characterization of the presence of sugars

In order to demonstrate the presence of sugars in each of the extracts, an acid hydrolysis is performed, which consists in mixing 5 ml of extract obtained previously in

1.1. with 10 ml of 6 M hydrochloric acid and 40 ml of ethanol containing 0.05% by weight of BHT (butylated hydroxytoluene). The whole is refluxed for four hours. After cooling to room temperature, the solution obtained is analysed using the reverse-phase liquid chromatography method described for the assay of the monomeric polyphenols in paragraph 1.2.1.U) above. The sugars present in the extract are, after this process, degraded and lead to the formation of 5-ethoxymethylfurfural, this compound being identified by its retention time on the chromatogram in comparison with an analytical reference of 5- (hydroxymethyl)furfural, abbreviated as 5HMF, sold by Aldrich, in a purity of 99%.

For the fruit and vegetable extracts, this peak is present, in particular for apples.

The presence of 5-ethoxymethylfurfural may also be revealed with a kit for the colorimetric assay (coloration from pale yellow to violet-red) of 5HMF commercially available from Merck (hydroxymethylfurfural tests 1.17952.001) and used in the agrifood industry, with the proviso of neutralizing the highly acidic medium and of diluting the highly alcoholic medium used in the sugar hydrolysis. This neutralization performed using a sodium acetate buffer makes it possible to adjust the pH to a value of between 4.5-5, which is compatible with the manufacturer's recommendations. To do this, the sugar hydrolysis solution is diluted five-fold to bring the HCl concentration to 0.24 M and the ethanol content to 16%. A second twofold dilution of the solution thus obtained is then performed with a 0.5 M sodium acetate solution. A solution whose pH is 4.7 and whose alcohol content is 8%, which are compatible with the conditions of use of the kit described in the instructions for use supplied by the company Merck, is thus finally obtained.

H) Quantification of the simple sugars by high-performance ionic chromatography (HPIC)

Assay of the constituent simple sugars of each extract is performed by ionic chromatography on a Carbopac® PlO column sold by Dionex, coupled to an amperometric detector integrated with a potential wave. The identification and quantification of the sugars are performed by external calibration, the standards being glucose, fructose and sucrose.

OPERATING CONDITIONS

- Column: Dionex Carbopac PAlO Guard 4x50 mm - Ref. 046115 and Dionex Carbopac PlO Analytical 4x250 mm - Ref. 046110 - HPIC eluent: 50 mmol/1 NaOH:

Preparation of the eluent The tank is filled with Milli-Q water. The assembly is degassed with helium for at least 15 minutes. 2.9 ml of sodium hydroxide per litre of water (NaOH Fisher S/4930/05 at 46%) are added and the assembly is degassed for about 15 minutes before being placed under pressure. - Temperature: 40⁰C

- Flow rate: 1.5 ml/min

- Volume injected: 25 μl

- Detection: Amperometry integrated with a potential wave. Measuring electrode: Au Reference electrode: Ag/ AgCl

- The potential wave selected is that recommended by the manufacturer for simple sugars.

To avoid excessive temperature variations, the column and the electrochemistry cell are thermostatically maintained. - Calibration solutions:

The sugars used for the establishment of their respective calibration curves are:

- Glucose (Fluka 49139) with an RT of about 5.2 min.

- Fructose (Sigma F-0127) with an RT of about 6.0 min.

- Sucrose (Fluka 84099) with an RT of about 7.0 min. - Lactose (Sigma L-3625) with an RT of about 10.0 min.

Calibration solutions at 16 and 40 μg/ml are prepared as follows: 20.0 mg [50.0 mg] of each standard are placed in a 50 ml graduated flask. The volume is made up with water or the eluent, and the whole is subjected to mechanical stirring until dissolution is complete. 2.0 mm are taken therefrom and placed in a 100 ml graduated flask. The volume is adjusted to 100 ml with water. This solution is filtered through a Pall-Gelman GxF/GHP 0.45 μm or equivalent.

Preparation of the test solutions

A mass of each of the extracts obtained above is weighed out accurately, after lyophilization (m), and dispersed in a volume (v) of water so as to obtain a final concentration that is within the calibration range. This solution is filtered through a Pall- Gelman GxF/GHP 0.45 μm filtered or equivalent. CALCULATION OF THE SUGARCONTENTS

The calibration curves are plotted, placing the values of the areas obtained on the chromatograms of the calibration solutions on the y-axis, and the concentrations (in mg/ml) in the calibration solutions on the x-axis.

CALCULATION OF THE CONCENTRATIONS FROM THE CALIBRATION CURVES The concentrations in the test solutions are deduced from the calibration curves using the following formula:

S - A

C =

B in which:

C: Concentration in the test solution (mg/mL) S: area of the peak on the test chromatogram

A: y-axis at the origin of the calibration curve. (The calibration curves are of the type: Y = BX+ A) B: slope of the calibration curve. (The y-axis at the origin A is equal to 0 if the curve is forced by zero).

CALCULATIONOF THE SUGARCONTENTS INTHE SAMPLE

The contents in the sample are given by the following convention: τ C x v T = x 100 m in which: T: Sugar content in the sample (in %)

C: Concentration in the test solution (mg/ml) v: Final volume after dispersion of the sample (in ml) m: specimen weight of the sample (in mg)

The results thus obtained and expressed per 100 g of lyophilized apples are given in Table 4 below. TABLE 4

The sugar contents thus obtained for all the analysed extracts are reported in Table 6 given below. The values therein are reported this time in grams per 100 g of fresh fruit or vegetable.

Hi) Characterization of the polyphenol '( s) / sugar (s) weight ratio

The (polypheno I/sugar) weight ratio of each variety may thus be calculated from the results obtained according to the methods described above in 1.2.1. i) for the total polyphenols and in 1.2.3. ii) for the sugars.

Table 5 given hereinbelow includes these reports.

1.2.3. Fruit acid content of the fruit and vegetable extracts i) Assay of the fruit acids of each extract by high-performance liquid chromatography by exclusion coupled to a UV diode array detector (LC-DAD)

Assay of all the organic acids is performed by reverse-phase liquid chromatography and exclusion on the following columns:

• Phenomex Rezex RFQ-Fast Fruit H+ (8%) 7.8x100 mm column. Ref. 00D-0223-KO, and • Chromolith performance RP-18e 3x100 mm column.

Ref. UM5044/009, coupled to a UV diode array detector of the Waters 2996 type between 190 and 250 nm. The eluent is used is a 5 mM sulfuric acid solution.

The identification and quantification were performed on the fruit and vegetable extracts obtained previously in 1.1., the standards used being malic acid solutions of 2 μg/ml to 400 μg/ml.

H) Assay of the L-malic acid by visible spectrophotometry This method via visible spectrophotometry first involves an enzymatic oxidation of L-malic acid with L-malate dehydrogenase (L-MDH).

More specifically, in the presence of nicotinamide adenine dinucleotide

(NAD), L-malic acid (L-malate) is oxidized to oxaloacetate via L-malate dehydrogenase (L-MDH) (reaction ©). The reaction equilibrium is located on the side of malate. By removing the oxaloacetate from the reaction medium, reaction © is shifted in the direction

L-malate — > oxaloacetate.

Removal of the oxaloacetate from the reaction medium is performed via the transformation of the oxaloacetate to L-aspartate (reaction ©) via glutamate oxaloacetate transaminase (GOT) in the presence of L-glutamate.

The formation of NADH, measured by the increase in absorbance at a wavelength of 340 nm, is proportional to the amount of L-malate. This method may be performed especially with the kit sold under the product code

KHPE035564 by the company Seppal, by following the protocol proposed with this kit.

The results for the L-malic acid contents thus determined in the fruit and vegetable extracts are reported in Table 5 given hereinbelow. The values therein are reported as mass percentages of acid relative to the total weight of the analysed extract.

1.3. Results: polyphenol, L-malic acid and sugar contents of the fruit and vegetable extracts

TABLE 5

* Folin content, in gallic acid equivalents per gram of fresh fruit extract. ND : not determined

The fruit and vegetable extracts prepared according to the protocol described in 1.1. and characterized according to the methods described in 1.2. are used in formulation compositions as described in the examples that follow.

The percentages of the ingredients in the compositions below are expressed by weight relative to the total weight of the said composition.

EXAMPLE 2:

Oil/water emulsion

*The 45 ml of apple extract and of extraction solvent obtained in Example 1 are used, for which the original MeOH/water solvent mixture is replaced with water.

Procedure: Phases Al and Bl are heated to 65⁰C. Phase Bl is poured into phase Al with high shear. The mixture is stirred vigorously for a few minutes and then cooled to 40⁰C. Next, phase C is introduced. The resulting mixture is cooled to room temperature and phase D is introduced to finish.

EXAMPLE 3:

Emulsified gel

* The 45 ml of apple extract and of extraction solvent obtained in Example 1 are used, for which the original MeOH/water solvent mixture is replaced with water.

Procedure: Phase Bl is mixed in the main tank. Phase Al is mixed in an additional tank. Phase Bl is poured into phase Al with high shear at room temperature. The mixture is stirred with high shear for a few minutes and phase C is then introduced, with continued stirring for 15 minutes.

EXAMPLE 4:

Emulsion

Procedure: Phases Al and Bl are heated to 65°C. Phase Bl is poured into phase Al with high shear. The mixture is stirred vigorously for a few minutes and then cooled to 40⁰C. Phases Cl, C2 and C3 are then introduced. The mixture is cooled to room temperature and phase D is introduced.

EXAMPLE 5:

Oil/water composition

Procedure: The lipid phase is mixed in a tank. The aqueous phase is mixed in an additional tank. The lipid phase is poured into the aqueous phase with high shear at room temperature. Stirring at high shear is maintained for a few minutes.

Claims

1. Cosmetic process for treating keratin materials, comprising the topical application to the said materials of at least one cosmetic composition, which is free of polyphenol oxidase and which comprises at least one polyphenol in combination with at least one sugar, the said polyphenol and the said sugar being derived from fruit or vegetables, with the said polyphenol being present in a proportion of less than 75% by weight, expressed as gallic acid equivalent, relative to the weight of the said composition, and the presence of the said sugar being detectable in the said composition via acid hydrolysis.

2. Cosmetic process for treating keratin materials, comprising the topical application to the said materials of at least one cosmetic composition, which is free of polyphenol oxidase, the said composition comprising at least one polyphenol in combination with at least one sugar, the said polyphenol and the said sugar being derived from fruit or vegetables, and the said sugar being present in a content of from 5% to 60% by weight relative to the total weight of the said composition.

3. Cosmetic process for treating keratin materials, comprising the topical application to the said materials of at least one cosmetic composition, which is free of polyphenol oxidase and which comprises at least one polyphenol in combination with at least one sugar, the said polyphenol and the said sugars being derived from fruit or vegetables and being used in a (polypheno I/sugar) weight ratio of less than or equal to 5.

4. Process according to any one of the preceding claims, in which the polyphenol and the sugar are used in the form of at least one extract of fruit or vegetables simultaneously comprising at least one polyphenol and at least one sugar.

5. Process according to any one of the preceding claims, in which the said composition comprises also at least one fruit acid derived from fruit or vegetables.

6. Process according to the preceding claim, in which the said fruit acid is present in an amount of greater than or equal to 0.05%, in particular ranging from 0.07% to 20% and more particularly from 0.1% to 10% by weight relative to the total weight of the said composition.

7. Process according to the claim 5 or 6, in which the said polyphenol, the said sugar and the said fruit acid are used in the form of at least one extract of fruit or vegetables simultaneously comprising at least one polyphenol in combination with at least one sugar and at least one fruit acid.

8. Process according to any one of the preceding claims, in which the said polyphenol is present in a proportion of less than 75% by weight, expressed as gallic acid equivalent, relative to the weight of the said composition, and especially in a content of less than or equal to 65% by weight, expressed as gallic acid equivalent, relative to the total weight of the said composition.

9. Process according to any one of the preceding claims, in which the said polyphenol and the said sugar are used in a (polypheno I/sugar) weight ratio of less than or equal to 3, advantageously less than or equal to 1 and even more advantageously less than or equal to 0.5.

10. Process according to any one of the preceding claims, in which the composition comprises a sugar content of greater than or equal to 6%, better still greater than or equal to 8%, even more advantageously greater than or equal to 12% and particularly greater than or equal to 15% relative to its total weight.

11. Process according to any one of Claims 5 to 10, in which the said polyphenol and the said fruit acid are used in a fruit acid/polyphenol weight ratio of greater than or equal to 0.02, preferably greater than or equal to 0.3, advantageously greater than or equal to 0.4 and even more advantageously greater than or equal to 1.

12. Process according to any one of Claims 5 to 11, in which the fruit acid is chosen from L-tartaric acid, malic acid, quinic acid, shikimic acid, citric acid, succinic acid, fumaric acid, lactic acid, suberic acid, glycolic acid, glutaric acid, acetic acid and malonic acid.

13. Process according to any one of Claims 5 to 12, characterized in that the fruit acid is malic acid, in particular L-malic acid.

14. Process according to any one of the preceding claims, characterized in that the fruit or vegetable(s) is (are) chosen from apple, lychee, apricot, grape, persimmon, pear, banana, avocado, bean, blackcurrant, blueberry, blackberry, cherry, cranberry, redcurrant, elderberry, grapefruit, kiwi, lentil, bilberry, mango, cherry, ginger, nectarine, onion, orange, kale, artichoke, asparagus, red cabbage, chive, aubergine, garlic, potato, parsley, peach, plum, radish, quince, suede, spinach, strawberry, mandarin, tomato, beetroot, broccoli, carrot, cauliflower, celery, guava, sweet potato, raspberry, medlar, papaya, pomegranate, pea, rice, kumquat, passion fruit, prickly pear (Opuntia cactus), Indian gooseberry, buddha's hand, yuzu, citron, mikan, limequat, lemon and mexicani, and mixtures thereof.

15. Process according to any one of the preceding claims, in which the fruit is (are) chosen from fruit of plants from the Rosacea family.

16. Process according to the preceding claim, in which the fruit of plants from the Rosacea family are of the genus Malus.

17. Process according to any one of the preceding claims, in which the fruit is chosen from apples chosen from Reinette de Cannes, Rambour d'Allemagne, Idared, Fuji, Fiorina, H. Dumont, Querina, Pomme de Bucey, Croque, Calville Rouge d'Ete, Nationale, Reinette d'Orleans, Nouvelle France, quince apple, Colapuy, Akane, Rambour d'Ete, Charden, Reinette Doree de Versailles, Rambour d'Hiver, Pommate d'Ervy, Reinette pepin, Baumann, Gala, Pomme Cloche, Estival, Jersey Mac, The Senator, Summered, Canada grey Reinette Bio, Calville du Roi, Benedictin, Judeline, Winter Banana, CuI d'Oison, Chataignier, Melrose, Api Etoile, Pomme Fraise, Avrolles, Limousine, Signe Tillish, Grand Alexandre, Pomme Raisin, Reinette Clochard, Doux Amer, Citron d'Hiver, Teint Frais, Cusset, Reinette d'Armorique, Reinette Franche, Antoinette, Genereuse de Vitry, Api Double, Archram and Kidds orange and mixtures thereof and/or from pears chosen from Doyenne du Cornice, Bergamote Crassane, Certeau d'Automne, Beurre Bachelier, Saint-Gilles, Colmar, Rateau, Beurre Clairgeau and Le Lectier, La Carisi, saussinet gris, petite grise, brie pear, Royale d'hiver, Sucree de Montlucon, Gros Noir, Petit Noir, Callouat, Catillac, Saint Lezin, Imperiale a feuilles de chene, Bergamotte de Parthenay, sage pear and Charles Cognee, and mixtures thereof.

18. Process according to any one of the preceding claims, characterized in that the said cosmetic composition also comprises at least one vitamin.

19. Cosmetic composition of emulsion type containing, in a physiologically acceptable medium free of polyphenol oxidase, at least 5% by weight of a liquid fatty phase and at least one polyphenol in combination with at least one sugar the said polyphenol and the said sugar being derived from fruit or vegetables.

20. Composition according to the preceding claim, comprising at least 10% by weight, or even advantageously from 15% to 60% by weight and especially from 20% to 50% by weight, of a liquid fatty phase.

21. Cosmetic assembly comprising:

(i) at least one container delimiting at least one compartment, the said container being closed by a closing member; and (ii) at least one composition (A) according to Claim 19 or 20, placed inside the said compartment.

22. Assembly according to the preceding claim, also comprising a composition (B) comprising at least one cosmetic or dermato logical active agent conditioned separately from the said composition (A).