NL8920746A - THE SKIN CELLS AGAINST LIGHT PROTECTIVE AGENTS (SKIN CYTO PHOTO PROTECTORS), IN PARTICULAR LONGER HANSCELLS BASED ON NUCLEIC ACID COMPLEXES, KNOWING RIBONUCLEOPHEDIC PROTECS, RIBONUCLEO-TIDENATIC PREPARENETLES AND RIBONUCLEOSPHARMOSPHONE. - Google Patents

Description

Title: The skin cells from light protective agents (skin cyto-photo-protectors), in particular of the Langerhans cells based on nucleic acid complexes, namely ribonucleoprotides, ribonucleotides and ribonucleosides, containing cosmetic or dermo-pharmaceutical preparations for topical use, as well as new connections in themselves.

The skin cells from light-protecting agents, in particular from the Langerhans cells, based on nucleic acid complexes, namely ribonucleoprotides, ribonucleotides and ribonucleosides, containing cosmetic or dermo-pharmaceutical preparations for topical use, and new compounds in themselves .

The invention essentially relates to a skin protecting agent from light protecting agents, in particular from the Langerhans cells based on complex nucleic acids, namely ribonucleoprotides, ribonucleotides and ribonucleosides, containing cosmetic or dermo-pharmaceutical preparations for topical use, as well as new compounds for example, consisting of associations with, preferably, biological, photoprotective agents, especially those contained in the epidermic having a direct photoprotective action, such as keratin, the urocaninates, certain amino acids, or an indirect action such as tyrosine-containing mixtures, tryptophan stimulators of the biosynthesis of melanin (which is known as one of the better natural photoprotectants against the harmful effects of sunlight or UV radiation).

Numerous light-protecting agents are already known in the art. For example, FR-A-2 026 267 describes the unified use with uracil of cytosine, guanine, and / or 5-chlorouracil as the skin lightening agents, whereby control tests on the light protection effect are given by determining the "mean protection factor "according to SCHULZE (Parfumerie und Kosmetik 37r 310/365 (1956)). The latter also discloses combinations of these materials which are purine and pyrimidine bases with conventional photo-protective agents such as cinnamates, in particular ethylhexyl p-methoxycinnamate.

However, these purine or pyrimidine bases have little or no water solubility.

Also known from the applicant's earlier patent EP-B-10 483 are tanning accelerators, thus leading to a light protection of the skin, based on arginine tyrosinate and provided in combinations with urocanic acid or arginine urocaninates. The browning accelerators have a light-protecting effect, because they stimulate the formation of melanin. FR-A-2 579 461 also describes amides of urocanic acid as a sunscreen.

From FR-A-2 511 243, it is also known the use of highly polymerized ADN in cosmetic preparations such as creams, milk or lotions, to improve the elasticity or regeneration of the cells. The patent discloses the possibility of protecting the skin from harmful sun rays. However, in the context of the sun milk it is proposed to add an ultraviolet resistant sun filter, which has been indicated not to be sensitizing.

None have been described by the author.

Furthermore, various nucleic acid derivatives have been described as such in certain cases with therapeutic uses primarily to control asthenia due to insufficient liver function (insufficientia hepatitis) (see FR-A-2 329 289; FR-A-2 181 220; US-A -3 326 892; AU-B-461 034; FR -Al 440 795; FR-A-2 354 774; FR-A-2 113 774; BSM-A-3 932; BSM-A-4 811).

All known photoprotective agents are intended to protect the skin from the dangers of excessive or prolonged solar radiation, the harmful effects of which are known to be primarily associated with ultraviolet rays of the UVB and UVA type. These harmful effects are known to manifest in the acute manifestation of simple solar erythema to skin necroses through varying degrees of burn; tardive effects from prolonged and repeated exposure leading to premature skin aging, finally long-term carcinogenic effects of the skin from long-term UVR exposures.

The protection from light has therefore long proven to be a necessity to protect against the harmful effects of the sun's rays.

For example, numerous so-called sunscreen cosmetics, which are intended to provide a guarantee against the harmful effects of the sun, have been applied topically and contain different varieties of photoprotectants or sunscreens, representative examples of which are described in the above-mentioned documents.

For consumers, the light-protective activity of these sunscreens is specified on the products, in that the light-protective index or S.P.F. (Sun Protecting Factor) is determined, determined on sets of volunteers of common photo types by official methods.

These methods rely in particular on the visual determination of the MED (Minimum Erythemal Dose) corresponding to the smallest UVR radiation dose capable of delivering visible erythema with clear edges using a solar simulator 24 hours after irradiation.

However, histological checks have shown that clearly before the onset of the delimited erythema, cell damage already occurred at significantly lower UVR doses than the MED. Thus, the SPF value is not adaptable to light protection of the cells. Thus, the appearance in the epiderm of completely characteristic "sunburn cells (Sunburn Cells") has been observed corresponding to UVR-mediated epiderm keratinocytes, at doses below the MED, therefore without the appearance of erythema being detected. Thus, cell damage in the skin can occur at UVR doses lower than those causing visible erythema, there is a clear interest not to be satisfied with ensuring protection from light, which allows to avoid solar erythema, but furthermore, effective protection from light of to insure the living cells of the epiderm or derm, which is not or poorly supplied by solar flashes, which is oriented to a simple MED of medium value, well known by the most changeable users.

Among these living cells that can be damaged by UVR, the following can mainly be mentioned: * For the epiderm:

The epidermal keratinocytes, essential for the protection of skin and in particular the Langerhand cells, fundamental element of the immune defense system of the skin. They play a fundamental role in collecting and treating the antigens:. exogenous antigens: for example, viras, toxins, sensitizers.

. endogenous antigens: abnormal or transformed or even malignant epidermal cells.

According to B. GILCHREST *, if the number of Langerhans cells and their functionality (tested with the DNCB test) decreases with age in covered zones (physiological aging), this aging is even more important with age in exposed zones compared to the covered areas (actinic aging).

This change with age of the number and function of the Langerhans cells, mainly associated with repeated sun exposures, entails a decrease in the skin's immunity defense system and particularly favors carcino and skin photocarcinogenesis.

Other epidermal cells involved: the MERCKEL cells and melanocytes, the number and vitality of which are declining with age, with a corresponding decline in the skin's ability to self-protect against light from melanin pigments.

* For the derm:

The fibroblast fibrocytes, which are responsible for the biosynthesis of the constituent elements of the derm.

Furthermore, the present inventors have appreciated verifying whether the sunscreen compositions and possibly the classic sunscreens, such as the cinnamates and PABA esters, might not have a cytotoxic or photo-cytotoxic effect on the living cells of the epiderm and / or of the derm, which they must ensure protection from light and in particular on the Langerhans cells, which are the essential element of the skin's immunity.

The present inventors have now unexpectedly discovered that the tested filters contacted with living epiderm and derm cells under in vivo and in vitro conditions were not only poorly tolerated but exhibited insignificant cytotoxicity, especially in in vitro control. As for the Langerhans cells, the commonly used filters behave as hapten and therefore block or alter the essential function of immunological response of the Langerhans cells. The process manifests itself, among other things, by blocking the HLADR site, which plays a major role in the recognition and location of the antigens.

The protection of the cells from light is now deviated if the photo-protective agent itself is cytotoxic or function-disrupting.

The observation of a cytotoxicity of known sunscreens tested in contact with the above-mentioned living cells suggests that the risk exists not only in cell cultures, but in vivo if these x) Barbara A Gilchrest-Skin Aging Processes-CRC-Press, 1984 p. 73. 87. 102. 103.

filters could pass through the skin by simple topical use.

Recent studies now conducted on various cinnamic acid esters, which are common photoprotective agents, show that when incorporated into cosmetic sunscreen excipients, these filters penetrate the skin relatively quickly, but were additionally present in the circulating blood (see M.R. CLAUS Denis presented to the University of Strasbourg, France (1982) with the title "Etude de la stabilité photochimique et de la pénétration cutanée d'esters de l'acide para-méthoxycinnamique").

Likewise, other publications of sensitization and allergic reactions (including the book by J. Foussereau entitled "Les eczémas allergiques, in the chapter: Les Anti-solaires" published by MASSON in 1987, in particular pp. 312-319, and also the MAYBACH article published in Contact Dermatitis 1978, pp. 1665-1666 entitled "Allergy Contact Photo-dermatitis to PABA; JEANMOUGIN's article published in Photo Dermatoses, p. 180 on contact allergies and photo-allergies, DAVIES 'article published in Contact dermatitis 1982, £, pp. 190-192 entitled "Acute Photo-sentivity from sunscreen 2, EE PMC; Horio's article published in Dermatologies 1978, 156. pp. 124-128 title "Photo Contact Dermatitis from PABA", the article by THOMSON and MAIBACH published in Arch. Dermatology, 1977, 113, pp. 1252-1253).

The present invention therefore aims to solve the new technical problem consisting in providing new specific (de) cells from light-protecting agents that can be used topically over long periods of time, which are cyto-compatible and well tolerated at even long-term topical use, such as for the products called "anti-aging" for daily use, preferably without the use of classic sunscreen filters.

The present invention also aims to solve the new technical problem consisting in providing new photo-protective agents with a specific activity of photo-light protection in cells, called cyto-photo-protection, especially for the cells essential of the epiderm and derm, such as the keratinocytes, the fibroblasts, and especially the Langerhans cells.

The present invention also aims to solve the new technical problem consisting in providing new skin cells to light-protecting agents, which do not or substantially do not behave as hapten, thus the essential function of immunological response of the Langerhans cells do not block.

The present invention also aims at solving these new technical problems outlined above by providing such new skin cells with photo-protective agents, which are additionally compatible and stable in most of the cosmetic or dermatological preparations, while preferably being water soluble , thus enabling better penetration into the epidermal layers, which allows to distinguish the bio-cyto-photo-protectors from the classic sunscreens.

These new technical problems are solved for the first time by the present invention in a manner that is also usable on an industrial scale.

Thus, in a first aspect, the present invention provides a skin cell photo-protective agent of biological or biotechnological origin, which in particular has a photo-protective activity of the Langerhans cells of the skin and which preferably does not contain a synthetic cytotoxic sunscreen in in particular of the type cinnamate or PABA or its derivatives, characterized in that it comprises at least one compound selected from the group of nucleic acid compounds and nucleic acid derivatives comprising: A - the ribonucleic acids as well as their derivatives, in particular their salts with mineral or organic bases and preferably the complex salts of basic proteins, basic amino acids or basic peptides; B - the ribonucleotides as well as their derivatives of the type of salts with mineral or preferably organic bases, including the complex salts with basic proteins, basic amino acids or basic peptides; and C - the ribonucleosides.

According to a special embodiment, the ribonucleic acids in the form of salts with mineral bases are advantageously selected from NaOH, KOH and NH4OH, or organic bases, in particular ethanolamines.

In another special embodiment, the ribonucleic acids are in the form of their salts with basic proteins, such as: the histones or microproteins with a molecular weight between about 11,000 and 24,000, which are strongly basic due to their wealth of basic amino acids of the arginine and lysine type, which make up up to 25% of the amine residues of these molecules. Preferred histones are those of the types H1, H2A, H3 and H4, which are listed, for example, on page 818 of the book by A. LEHNINGER. Such histones are especially found in the sperm of certain fish, white blood cells, the thymus and more commonly in many cell nuclei; the globins whose molecular weights range from about 15,000 to about 70,000 and are rich in histidine (5-9%) and lysine basic amino acids.

In another special embodiment, the ribonucleic acids are in the form of their complex salts with basic amino acids, preferably selected from L-histidine, L-arginine, L-lysine, L-hydroxylysine and L-ornithine.

In another variant, the ribonucleic acids are in the form of their salts with basic peptides.

In addition, it should be noted that the above-mentioned ribonucleic acid complexes have the advantage of being water-soluble, exhibiting good diffusion ability in the epiderm and they can be used in concentrations that allow to obtain biocompatible pH values between 5 and 5 preferably. , 8 and 8, while the interstitial fluid environment has a pH of about 7.4.

According to another special embodiment of the invention, the above-mentioned ribonucleotides are selected from the group of the common mono-ribonucleotides, i.e. the normal constituents of the corresponding nucleic acids, which exhibit a strong UV absorbing capacity in the wavelengths 250-280 nm.

The preferred ribonucleotides are the following:

AMP ADP ATP

GMP GDP GTP

CMP CDP CTP

UMP UDP ÜTP

IMP IDP ITP

XMP XDP XTP

Preferably, the above-mentioned ribonucleotides are used in the form of their salts with bases, making it possible to obtain pH values of the order of 5.8-8, which are biocompatible.

In a special embodiment, the above-mentioned ribonucleotides are in the form of their salts with mineral bases, preferably selected from NaOH, KOH and NH4OH, or with organic bases, in particular the ethanolamines.

An example of a particularly preferred salt is the sodium salt of the ATP, specific for the light-protecting effect of Langerhans cells.

In another special embodiment, the above-mentioned ribon cleotides are in the form of their basic protein salts, such as: the histones or microproteins of molecular weight between 11,000 and about 24,000. In particular, it concerns histones of the types H1, H2A, H3B, H3 AND H4 as previously described.

the globins or coupled proteins of hemoglobins and myoglobins whose molecular weights are between about 15,000 and about 70,000.

According to another special embodiment of the invention, the above-mentioned ribonucleotides in the form of their salts with basic amino acids, in particular with one or more basic amino acids, are selected from the group consisting of L-histidine, L-arginine, L-ornithine, L- hydroxylysine, and L-lysine.

In another variant, the ribonucleotides are in the form of their salts with basic peptides.

In another special embodiment, the above-mentioned ribonucleosides are selected from the group consisting of the common mono-ribonucleosides, which are the normal constituents of the corresponding nucleic acids, which exhibit a strong UV absorbing power in the wavelengths of 250-280 nm, preferably :

RIBONUCLEOSIDES

. Adenosine. Cytidine. Guanosine. Iosine. Uridine. Xanthosine

The advantage of the ribonucleosides is that they usually exhibit direct pH values that are compatible with skin cell physiology, therefore do not a priori require the formation of salts, complexes or biochemical combinations with basic proteins, basic peptides and basic amino acids.

These nucleosides may, in certain embodiments, be combined or combined with one or more of the above-mentioned nucleoprotides or ribonucleotides or their salts, calculated in amounts to obtain biocompatible pH values between 5.8 and 8.

It is understood that it is preferred according to the invention to use water-soluble photoprotectants which are readily diffusible in the epiderm at concentrations enabling biocompatible pH values to be obtained or between 5.8 and 8.

It should be noted that the nature of the nucleic acid AEN or of the poly-ribonucleotides used to form the derivatives of the invention may be arbitrary. These may be starting poly-ribo-nucleotides whose secondary or tertiary structure has been retained, but also ribonucleic acids resulting from the more or less partial denaturing of the poly-ribo-nucleotides, because these more or less partial denaturing is not bothersome. Thus, one can use acids, the primary structure of which can be maximally retained, or the product of the more or less spared denaturing degradation of these primary structures, resulting in fragments of primary structure, going from the poly to oligo and to the mono nucleotides and / or to the corresponding poly, oligo or mono ribonucleosides.

This more or less partial denaturing does not hinder the formation of the derivatives of the invention used as cyto-photo-protectors, because this use is not intended to use the original genetic code * of the ARN used for the preparation of the derivatives according to translate the invention.

From the above, it follows that the purpose of the topical use of the derivatives of the invention is to exert cytotoxic protective effects by applying the compounds of the invention to or in the top skin layers.

They thus play the role of chromophores or of the most advanced passive targets, which absorb and capture the energy of the radiation competitively and preferentially, thus preventing the rays from reaching the potential targets which must be substantially protected from the damage of the rays, formed by the active cell organites and constituent macro molecules.

In addition, the presence of the compounds of the invention in an important amount, including poly-, oligo- and mono-ribonucleotides, salts, complexes, combinations and derivatives of poly-, oligo- and of mono-ribonucleosides is very well tolerated by the cells because they are naturally found to contain a high percentage of between 5 and 15%, based on the dry weight of the living cells, and are normally found in the corneal epidermis layers.

The compounds according to the invention are therefore biological substances, homologous or analogous to the substances naturally present in the epiderm.

It is recommended to use the derivatives of the ribonucleic acid or of the components of the ARN relative to the derivatives of the ADN due to the fact that: - the ARN and its derivatives are naturally present in the eucaryot cells in concentrations usually 2-8 times stronger than the derivatives of ADN and thus approaching the cell and tissue physiological environment more closely, - the ARN and ribonucleo derivatives appear to be less sensitive to UVB radiation, - the ARN are more labile to depolymerization and partial hydrolysis to nucleotides of their molecule than the ADN, which is beneficial for the cytotoxic protection of the skin, - the ARN are as indispensable for the normal functioning of the skin cells as the ADN and the proteins of these same cells.

According to another special embodiment of the invention, the cytotoxic protective agents of the skin according to the invention are characterized in that they additionally contain derivatives of urocanic acid or urocanoprotides, because these derivatives show a synergistic effect with the aforementioned ribonucleoprotides, ribonucleotides and ribonucleosides.

These urocanic acid or urocanoprotide derivatives are simple salts or complexes of urocanic acid or of urocanic acid derivatives with certain proteins, peptides, amino acids.

These derivatives of urocanic acid or urocanoprotides in the form of complex salts are preferably obtained by a combination of urocanic acid with: a) basic proteins, advantageously histones or globins, in particular as previously described; b) light absorbing ribonucleotides such as AMP, ADP and ATP; c) basic peptides, d) basic amino acids, preferably L-histidine, L-arginine, L-lysine, L-hydroxylysine and L-ornithine, individually or in combinations.

It will be understood that the purpose of this biochemical combination is to realize water soluble biological complex salts as opposed to the urocanic acid which is little or insufficient and more cyto compatible than the urocaninates of Na, K.

These urocanic acid derivatives develop a very high UVR absorbency especially in the bands 265, 290-320 nm, which compounds are the more UV absorbing as they are combined with ribonucleotides, proteins, peptides and amino acids, which are themselves light absorbing comprising an absorption band extending from 265-320 nm.

They are important in that they are soluble, clearly substantive, and their solutions can be adjusted to physiological pH values of 6.0-8.0 depending on the amounts of each of the ingredients.

Another unexpected particularly beneficial effect of the cytoprotective protectors of the invention lies in the fact that the combination of the urcanic acid derivatives with the cytoprotective protectors of the invention achieves a natural process of light defense of the skin . It can be observed that the amount of the salts and urocanin complexes increases significantly up to 10 times in the epiderm and in particular in the reservoir part of the stratum corneum after the solar irradiation and due to the thermal stimuli of the sweat glands by the infrared rays of the sun.

According to the invention, urocanin derivatives are preferred for the urocanoprotidic complexes, namely the basic urocano-histones, urocano-peptides and urocano-amino acids and urocano-nucleotides that are more cytophilic than the derivatives or mineral alkali or alkaline earth salts .

According to another special embodiment of the invention, the cyto-protectors of the skin according to the invention additionally contain amino acids and peptides or proteins.

Advantageously, these amino acids and peptides and proteins are selected from: 1) one or more of the 20 common ordinary amino acids of the proteins, the list of which is below:. Amino acids involved in the aforementioned complexes and combinations L-histidine, L-arginine, L-lysine, L-citrulline, L-ornithine and L-hydroxylysine.

. Aromatic amino acids: L-tyrosine, L-phenylalanine, L-tryptophan. Very advantageous because self-possessing an important UV-absorbing effect in the band-280 nm.

. Amino Dicarboxylic Acids: L-Glutamic Acid, L-Aspartic Acid.

. Cyclic amino acids: L-proline * (L-hydroxyproline).

. Amino monocarboxylic acids: glycine, alanine, L-valine *, L-leucine *, L-isoleucine.

. Hydroxy amino acids: L-serine *, L-threonine *.

. Amino acid amides: L-glutamine *, L-asparagine.

. Sulfur-containing amino acids and sulfur-containing oligo-peptides: L-cysteine *, L-methionine *, cystine *, * Epiderm amino acids which are abundant in the keratin of which the light-protective capacity is known.

2) One or more of the usual peptides and proteins of the cells and / or peptides resulting from the acidic, basic or enzymatic hydrolysis of polypeptides and / or proteins, scleroproteins and soluble proteins.

For example: GLUTATHION: tripeptide which is very soluble in water and usually present in all living cells in high concentration (5 mM) and which plays an important role in the intracellular transport of the amino acids and in the biological red-ox- reactions.

The hormonal peptides are excluded from the present invention. On the other hand, the. Scleroproteins and their partial hydrolysates.

For example: silk fibroin concentrations of 1-10% collagen concentrations of 1-10% elastin concentrations of 1-10% hydrophilic keratins. Soluble proteins and their partial hydrolysates: For example: (in concentrations of 0.10-10%) - histones - globins (hemoglobins and myoglobins) - plasma proteins (eg serum albumin and serum globulins) - partially hydrolysed plasma proteins (enzymatic pathway) either from plasma rich in proteins (about 8%) useful as a synergistic biological solvent for protection against light and biological transporter due to the osmotic pressure it develops, especially active and at its original pH of 7, 4 to dissolve and diffuse the aforementioned ribonucleo derivatives.

The importance of these peptides and proteins is that they themselves have a light absorbing capacity in the ultraviolet spectrum: in the zone 250-300 nm (absorption resulting mainly due to the presence of the 3 aromatic amino acids: tyrosine-tryptophan-phenylalanine), in the zone 210-250 nm (absorption mainly due to the amino acids: cysteine, methionine and histidine), the zone below 210 nm (absorption due to the peptidic bonds), and that they can be used synergistically with all the aforementioned nucleoprotides and all the aforementioned urocanoprotides thus enhancing the photo-protective ability of the former.

The present invention, according to a second aspect, covers the cosmetic or dermo-pharmaceutical preparations with the skin cells against photo-protective activity, in particular premature aging of the skin anti-activity, in particular protection of the Langerhans cells, characterized in that they contain at least one cyto photo protector as previously described.

In those cosmetic or dermo-pharmaceutical compositions of the invention, the total concentration of photoprotectants of the invention is usually similar to the concentrations of such known photoprotectants used to protect the skin from light. This concentration of active substance or active substances according to the invention will advantageously be between 0.01% and 10% by weight, preferably 0.1-3%, based on the total weight of the cosmetic or dermo-pharmaceutical preparation.

Any type of excipient customary for such cosmetic or dermo-pharmaceutical preparations for topical use can be used.

According to a third aspect, the invention also relates to new compounds, characterized in that it concerns compounds selected from the group consisting of: A - The simple or complex salts of the aforementioned ribonucleic acids with organic bases, selected from the groups consisting of basic proteins such as histone, globin, basic peptides or peptides such as glutathione. B - The simple or complex salts of the aforementioned ribonucleotides with the organic bases selected from the groups consisting of the aforementioned basic proteins and basic peptides.

According to a variant, the ribonucleotides are selected from:

AMP ADP ATP GMP GDP GTP CMP CDP CTP UMP UDP ÜTP IMP UDP ITP XMP XDP XTP

Finally, in a fourth aspect, the invention also relates to a method for preparing a skin-protecting agent, in particular of the Langerhans cells, characterized in that at least one compound is selected from the group consisting of a cyto-photo protector from the previously described compounds and nucleoprotidic and ribonucleosidic derivatives. The special embodiments for the preparation of these skin cells from light-protecting agents also result from the foregoing description.

According to a special embodiment of the method for the preparation according to the invention, the salts of the ribonucleic acids are prepared with mineral or organic bases, or rather the complex salts with basic proteins, amino acids or basic peptides as described above, according to a complete or partial classical acid -base reaction, in case of complex salts.

In another embodiment of the method of the invention, the salts of the ribonucleotides with mineral or organic bases comprising complex salts with basic proteins, basic amino acids or basic peptides, as previously defined, are also prepared according to a classical acid-base reaction.

The present invention also relates to a method for the preparation of cosmetic and / or dermo-pharmaceutical preparations, characterized in that at least one of the skin cells against photo-protective agent as previously defined is incorporated in a cosmetologically and / or pharmaceutically acceptable excipient or carrier.

Other objects, features and advantages of the invention will become apparent in light of the description below, with reference to the many examples of the invention, which are given by way of illustration only and in no way limit the scope of the invention. In the present description, and especially in the examples, all percentages are by weight unless stated otherwise.

EXAMPLE 1

Preparation of a mineral base ribonucleate

For example, a potassium ribonuclate is prepared in the following manner: 5.7 ml KOH 0.5 N is used to dissolve 1 g ARN pre-dispersed in 2 g distilled water.

A solution with a pH of 6.85 is thus obtained.

This addition of ribonucleic acid is done with vigorous stirring for several minutes.

The potassium ribonucleate thus prepared is separated in the following manner: in order to obtain the potassium ribonucleate in the form of a white pale yellow powder, it is sufficient to lyophilize the solution quickly. The following physicochemical characteristics are obtained: - ultraviolet spectrum (distilled water) = maximum 260 nm, pH (aqueous solution) prepared as before = 6.85.

The potassium ribonuclate or ammonium ribonuclate is prepared in the same way starting from the corresponding mineral bases NaOH and NH4OH.

EXAMPLE 2

Protein ribonucleate

The histone ribonucleate is prepared using, for example, ARN (CODEX grade) which is commercially available.

An aqueous solution of histone (type IV rich in Arginine) is prepared.

ARN in small amounts is added to this aqueous solution with stirring and stirring is continued until complete dissolution and a pH of 6.8 is obtained.

The histone ribonucleate obtained is separated by lyophilization or by precipitation with 96 ° ethanol. Spin, wash with anhydrous ethanol and dry in vacuo. The ultraviolet spectrum has a wavelength of 258-262 nm.

EXAMPLE 3

Basic amino acid ribonucleate The ribonucleates of arginine, histidine and lysine are prepared.

3 - A - Ribonucleate of aroinine - 0.665 g of L-arginine is dissolved in an Erlenmeyer flask by stirring in 100 ml of distilled water.

- 1.335 g of ARN CODEX is gradually added in small fractions with stirring at the temperature of the laboratory.

Stirring is continued until complete dissolution (approximately 1 hour).

The liquid obtained is filtered and dewatered, for example by lyophilization: a white powder is obtained.

(Yield about 95%).

. Ultraviolet spectrum (distilled water): maximum 258 nm. pH (distilled water): 6.3.

3 - B - Ribonucleate of histidine

0.947 g of L-histidine are dissolved in a conical flask by stirring in 100 ml of distilled water.

- 1.053 g of ARN CODEX is gradually added in small fractions with stirring at the temperature of the laboratory.

Stirring is continued until complete dissolution (about 12 hours).

The liquid obtained is filtered and dewatered, for example by lyophilization; a white powder is obtained.

(Yield about 95%).

. Ultraviolet spectrum (distilled water): maximum 258 nm. pH (distilled water): 6.4.

3 - C - Ribonucleate of lysine

0.619 g of L-lysine is dissolved in a conical flask by stirring in 100 ml of distilled water.

- 1.481 g of ARN CODEX are gradually added in small fractions with stirring at the temperature of the laboratory.

Stirring is continued until complete dissolution (about 1 hour).

The liquid obtained is filtered and dewatered, for example by lyophilization: a white powder is obtained.

(Yield about 95%).

. Ultraviolet spectrum (distilled water): maximum 258 nm. pH (distilled water): 6.2.

EXAMPLE 4

Mineral base ribonucleotidate Proceeding in the general manner as described in Example 1, the mineral base ribonucleotidates are prepared as follows: 4 - A. Sodium cytidine monophosphate.

4 - B. Sodium uridine monophosphate ..

4 - C. Sodium inosine monophosphate.

4 - D. Sodium adenosine diphosphate.

4 - E. Sodium adenosine triphosphate.

4 - F. Sodium guanosine monophosphate.

4 - G. Sodium adenosine monophosphate.

EXAMPLE 5

Protein ribonucleotidate The following protein ribonucleotidates are prepared by the following method: Cytidine-histone monophosphate.

The preparation takes place as follows. Since the cytidine monophosphate is highly soluble in water as is the histone, it is sufficient to prepare 1% solutions, respectively, and mix them to obtain a pH between 6 and 7 and then lyophilize the resulting preparation.

Absorption ÜV averaged 270 nm.

EXAMPLE 6

Ribonucleotidate of peptide The following ribonucleotidates of peptide are prepared:

The cytidine protamine monophosphate by the same method as in Example 5.

EXAMPLE 7

Ribonucleotidate of amino acid The following ribonucleotidates of basic amino acids are prepared: 7 - A - Cytidine aroinine monophosphate

In a conical flask, 0.857 g of L-arginine is dissolved by stirring in 100 ml of distilled water.

1.143 g of cytidine monophosphate are gradually added in small fractions with stirring at the temperature of the laboratory.

Stirring is continued until complete dissolution.

- The resulting solution is filtered and dewatered, for example by lyophilization.

A beige powder is obtained.

(Yield about 95%).

. Ultraviolet spectrum (distilled water): maximum 272 nm. pH (distilled water): 6.2.

7 - B - Cytidine-histidine monophosphate

1.07 g of L-histidine is dissolved in a conical flask by stirring in 100 ml of distilled water.

0.93 g of cytidine monophosphate are gradually added in small fractions with stirring at the temperature of the laboratory.

Stirring is continued until complete dissolution.

The resulting solution is filtered and dewatered, for example, by lyophilization.

A beige powder is obtained.

(Yield about 95%).

. Ultraviolet spectrum (distilled water): maximum 272 nm. pH (distilled water): 6.2.

7 - C - Adenosine arginine triphosphate.

In a conical flask, 0.966 g of L-arginine is dissolved by stirring in 100 ml of distilled water.

2.034 g of sodium adenosine triphosphate are gradually added in small fractions with stirring at the temperature of the laboratory.

Stirring is continued until complete dissolution.

- The resulting solution is filtered and dewatered, for example by lyophilization.

- A beige powder is obtained.

(Yield about 95%).

. Ultraviolet spectrum (distilled water): maximum 260 nm. pH (distilled water): 6.7.

7 - D - Adenosine histidine triphosphate - In a conical flask, 1 g of L-histidine is dissolved by stirring in 100 ml of distilled water.

- 1 g of sodium adenosine triphosphate is gradually added in small fractions with stirring at the laboratory temperature.

Stirring is continued until complete dissolution (about 1 hour).

The resulting solution is filtered and dewatered, for example, by lyophilization.

- A beige powder is obtained.

(Yield about 95%).

. Ultraviolet spectrum (distilled water): maximum 259 nm. pH (distilled water): 6.6.

EXAMPLE 8 Ribonucleosides

The ribonuclosides below are commercially available: 8-A. Adenosine.

8 - B. Cytidine.

8 - C. Iosine.

8 - D. Uridine.

8 - E. Uridine / cytidine (50/50).

EXAMPLE 9

Protein urocaninate

The histone urocaninate is prepared by proceeding in a manner similar to the preparation of the protamine urocaninate described in Example 10, but by operating at a temperature <50 ° C.

EXAMPLE 10 Uracaninate of Peptide

The urocanate of protamine is prepared in the following manner:

1.40 g of protamine is dissolved in a conical flask by stirring in 100 ml of distilled water.

1.40 g of urocanic acid is added gradually.

Stirring is continued at 70 ° C until complete dissolution. It is filtered and dehydrated, for example by lyophilization.

A beige powder is obtained.

(Yield about 90%).

. Ultraviolet spectrum (distilled water): maximum 269 nm.

EXAMPLE 11

Basic amino acid urocaninate The urocaninates of arginine and histidine are prepared in the following manner:. Arcrinin urocaninate - 720 g of methanol, 135 g of distilled water are added to a reactor equipped with a refluxing apparatus and 69 g of urocanic acid and 87 g of arginine are added with stirring.

The reaction mixture is heated slowly and heating is continued until reflux; stirring is maintained until complete precipitation.

- The mixture is cooled, then centrifuged and dried.

(Yield about 90%).

. Ultraviolet spectrum (distilled water): maximum 267 nm. pH (distilled water): 7.4.

. Histidine urocaninate previously described

Bring into a reactor equipped with a refluxing device of 720 g of methanol, 135 g of distilled water and adding with stirring 69 g of urocanic acid and 78.57 g of histidine.

Slow heating of the reaction mixture, continuing heating to reflux; maintaining stirring until complete precipitation.

Cool the mixture, then centrifuge and dry.

(Yield about 90%).

. Ultraviolet spectrum (distilled water): from 260-268 nm.

A series of examples now follows concerning compositions in the form of soluble amorphous powder enabling the preparation of solutions in distilled water at different concentrations with biocompatible pH values, for example between 6 and 7.5.

EXAMPLE 12 of a composition. Histidine ribonucleate 31.65

Histidine chlorohydrate 18.33

Lyophilized partial collagen hydrolyzate 50.02

Ultraviolet spectrum (distilled water) from 260-268 nm, depending on the nature of the collagen pH 6.0-6.8.

EXAMPLE 13

Composition Form: amorphous powder

Histidine ribonucleate 31.65

Cytidine / uridine 16.65

Histidine chlorohydrate 18.33

Dehydrated collagen hydrolyzate 33.37 EXAMPLE 14

Composition Form: amorphous powder

Histidine ribonucleate 47.83

Sodium ribonucleate 8.15

Arginine urocanate 16.66

Uridine / cytidine 1.32

Dehydrated collagen hydrolyzate 26.04 EXAMPLE 15

Composition Form: amorphous powder

Arginine ribonucleate 26.00

Histidine urocaninate 15.63

Arginine chlorohydrate 1.03

Histidine chlorohydrate 24.67

Dehydrated collagen hydrolyzate 17.02 uridine / cytidine 16.65 EXAMPLE 16

Composition Form: amorphous powder

Histidine ribonucleate 31.65

Histidine 18.33

Arginine urocaninate 16.65 uridine / cytidine 16.65

Hydrated collagen hydrolyzate 16.72 PREVIOUS, D 17

Composition Form: amorphous powder

Histidine ribonucleate 31.65

Histidine 18.33

Arginine urocanate 16.65

Lyophilized Collagen Hydrolyzate 33.37 EXAMPLE 18

Composition Form: amorphous powder

Arginine ribonucleate 37.50

Arginine urocaninate 35.67

Histidine urocaninate 20.00

Glutathione 1.25 L-tyrosine 3.00 L-phenylalanine 0.50 L-tryptophan 0.75 L-histidine 1.33 pH in distilled water = 6.5-7.

EXAMPLE 19

Composition Form: amorphous powder

Arginine ribonucleate 37.50

Arginine urocaninate 35.67

Histidine urocaninate 20.00

Glutathione 1.25 L-tyrodise / L-phenylalanine / L-tryptophan 4.25

Histidine Chlorohydrate 1.33 EXAMPLE 20

Composition Form: amorphous powder

Adenosine 0.04

Guanosine 0.04

Iosin 0.04

Cytidine 0.04

Uridine 0.04

Glucose 9.40

Arginine urocaninate 15.00

Lyophilized Blood Plasma Hydrolyzate 75.04 EXAMPLE 21

Sodium ribonucleate 20.00 CMP of arginine 1.70 GMP of histidine 1.70 UMP, sodium salt 1.00

Glucose 2.50

Keratin hydrolyzate 73.10

The base compositions form compositions of cytoprotective protectors of the invention and can be included as active substances in doses between 0.01% and 5%, exceptionally + 10% and preferably from 0.10 to 3% in dermatological , cosmetological and dermo-pharmaceutical preparations to form cosmetic or dermo-pharmaceutical preparations according to the invention.

This recording is carried out in a very simple manner, usually by dissolving in the aqueous phase of these preparations at temperatures between 20 ° C and 70 ° C.

Any type of conventional excipient of such cosmetic or dermo-pharmaceutical compositions containing water can be used. These can be aqueous lotions, aqueous gels, emulsions, ointments, creams, spreads, capsules.

In addition, these actives can be incorporated into liposomes, micelles and other microencapsulation to accelerate or delay penetration.

Below, a preparation example of a cosmetic and / or dermo-pharmaceutical preparation containing one of the aforementioned compositions constituting the subject of the invention is given.

It will be understood that the same can be done with the other compositions.

For example, the composition of Example 13 is included at a dose of 1% in the emulsion below: Prolylene glycol stearate SE 1.00

Paraffin oil 7.70

Stearin 1.50

Stearyl alcohol 0.40

Glycerol 4.00

Carbomer 934 0.10

Triethanolamine 0.80

Preservative qs

Distilled water qsp 100.00

TEST RESULT

In order to demonstrate the advantages of the cytoprotective protectors according to the invention, experiments have been carried out therein in comparison with the classical photoprotectors, aiming at evaluation - on the one hand of their own cytotoxicity - on the other hand of their light-protecting ability contact with the cells.

Thus, the results obtained with some of the compounds listed in the examples of the previous pages are combined in the following three tables.

It is noted that from a viewpoint of ability to protect the skin from light of these compounds compared to the methods of SCHULTZE or variants based on the MED, therefore the radiation dose for the appearance of a limited erythema, the protective anti-solar forces, which can be obtained between weak to medium indices layers.

In contrast, from the viewpoint of appreciation of the protection from light by in vitro contact, the cytotoxic protectors currently claimed are free of cytotoxicity at useful concentrations and exert substantial protection against sunlight and are essentially UV -B, at radiation levels normally tolerated by each user relative to their MED.

It is further noted that a comparative test conducted with a sodium salt of deoxyribonucleic acid does not provide significant cytotoxic protection. It is therefore surprising and not at all obvious to the skilled person that the organic derivatives of ribonucleic acid according to the invention, on the other hand, have a photo-protective effect.

On the other hand, it is known that the UV-B involves a morphological and functional breakdown of the Langerhans cells and it is known that the conventional sunscreens, type cinnamate, PABA do not prevent this breakdown.

Likewise, it is known that the UV-B carries a radiation of the ATP activity of the Langerhans cells, but this degradation cannot be prevented by the aforementioned sunscreens.

These same filters are ineffective to protect the Langerhans cells from degradation and negation of the response to the immunological test with DNFB by the UV-B.

PROTOCOL type I.

DL50 on MRC5 fibroblasts, in vitro. The MRC5 Fibroblast cells are inoculated on the EMEM environment, which is supplemented with fetal calf serum (5%).

. 24 hours later, the medium is replaced with a saline solution (PBS) of the product to be tested (in the case of the filters PMCEH and PABEH, prepared with a mother solution).

. A sufficient number of dishes is prepared by introducing increasing dilutions of the test substance (from 0.01% to 0.03%) to allow for a series of studies.

. All dishes are then incubated at 37 ° C for 2 hours.

. The saline solution is then replaced with the usual growth medium (EMEM + 5% SVF).

. 72 hours later, the cell cultures are stained.

. The number of living cells is evaluated by measuring the color intensity of each dish with the electronic image analyzer.

. The DL50 corresponds to the dose of the tested product just sufficient to inhibit the growth rate of the cells by 50% relative to the control.

PROTOCOL type II Toxicity to fibroblasts MRC5. The MRC5 cells are seeded on the classical culture medium.

. 24 hours later they are contacted with the product to be tested, which has been previously dissolved in PBS.

. The solution is then replaced by the growth medium = EMEM + 5% SVF.

. 3 days later, the growth rate is evaluated: - by measuring the color with the electronic image analyzer, or - by measuring the intracellular ATP percentage.

PROTOCOL type III

DL50 on epidermal keratinocytes, in vitro. The isolated epiderm keratinocytes are grown on dishes (culture of the explant) in the DMEM medium with 10% SVF.

. 24 hours later, the previous culture medium is replaced with an amino acid enriched saline (= DMEM) of the product to be tested.

. A sufficient number of dishes are prepared to achieve a series of increasing dilutions of the test substance.

. All dishes are incubated at 37 ° C for 3 days.

. Then, the intracellular adenosine triphosphate is extracted and its content in each dish is determined by the bioluminescence technique.

. The toxicity of each tested substance is expressed in percent based on the control environment (DMEM).

. The lethal dose (DL50) is graphically determined as the minimum dose of the product that decreases the percentage of ATP by 50% relative to the control.

EXAMINATION OF CY 5 TOXICITY DL 5Q

RESEARCH ON CYTOTOXICITY ON LONGER HANSCELLS (L.C.)

PROTOCOL IV

Evaluation of the cells' light-protective capacity of substances in contact with MRC5 fibroblasts. The aim of this study is to evaluate the photo-protective powers of various substances on the growth of MRC5 fibroblasts in cultures in vitro, when irradiated with a UVB light source.

. The cells are seeded in a small amount.

. 24 hours later, the MRC5 cells are covered with a solution of the test substance in the PBS and then irradiated with an exactly determined dose (in mJ / cm2) of UVB.

. The saline solution is then replaced by the growth medium EMEM + 5% SVF.

. 72 hours later, the cell culture is grown and the growth rate is evaluated with the electronic image analyzer.

PROTOCOL V

Investigation of the cells' photo-protective ability of substances in contact with Langerhans cells

Microscopic count of the Langerhans cells HLA-DR +. A suspension of epiderm cells is prepared from a skin biopsy.

. This cell suspension is divided into two parts:. 1 / one part serves as a control to which only the buffer PBS is added.

a) the first batch is not irradiated, b) the second batch is irradiated with UVB (x mJ / cm2).

. 2 / the other part receives the test substance dissolved in the buffer a) 3rd batch not irradiated, b) 4th batch irradiated with UVB (x mJ / cm2).

. The 4 aforementioned batches of epiderm cells containing Langerhans cells are then labeled by immunocytochemistry (labeling of the HLA-DR specific antigenic sites of the Langerhans cells).

. For each of the 4 lots, the HLA-DR cells are then counted by microscopic count.

. Results: - the first batch: Corresponds to the original number of intact L.C. HLA-DR + per unit volume.

- the 2nd lot: Irradiation with an exactly determined dose of UVB causes a reduction of the original number.

L.C.-HLA-DR + per unit volume.

The remaining number of L.C.-HLADR + = N lot 2.

- 3rd party: the substance suspected to be the L.C. Protecting from light may optionally exert specific cytotoxicity at a given concentration. The value determined is that of the number of L.C.-HLADR + remaining per unit volume in contact with the substance at the concentration tested. The corresponding number of L.C.-HLADR + = N-lot 3.

- 4th batch: allows to determine the number of L.C.-HLADR + in contact with the test substance at a concentration identical to the 3rd batch and after UVB irradiation with the same dose as the 2nd batch. The remaining number of L.C. — HLADR + per unit N-lot volume 4.

RESEARCH ON THE CELLS AGAINST LIGHT PROTECTION IN COt

x: maximum of the cells against light protective capacity = 100% NS: not significant

Claims (27)

1. Skin cells from photo-protective agent of biological or biotechnological origin, which in particular has a specific photo-protective activity of the functional cells of the skin, in particular of the Langerhans cells, which preferably does not contain a synthetic cytotoxic sunscreen, in particular of the cinnamate or PABA type or its derivatives, characterized in that it comprises at least one compound selected from the group of nucleic acid compounds and nucleic acid derivatives comprising: A - the ribonucleic acids, as well as their derivatives, in particular their salts with mineral or organic bases and preferably the complex salts of basic proteins, basic amino acids or basic peptides, B - the ribonucleotides as well as their derivatives of the type of salts with mineral or preferably organic bases including the complex salts with basic proteins, basic amino acids or basic peptides, and C-ribonucleosides. The light protection cell according to claim 1, characterized in that the ribonucleic acids are present in the form of salts with mineral bases, advantageously selected from NaOH, KOH and NH4 or with organic bases, in particular the ethanolamines. The light-protecting cell according to claim 1, characterized in that the ribonucleic acids are present in the form of their salts or complexes with basic proteins such as: the histones or microproteins with a molecular weight between 11,000 and about 24,000, the globins of which the molecular weights are between about 15,000 and about 70,000. The cell light-protecting agent according to claim 1, characterized in that the ribonucleic acids are in the form of their complex salts with basic amino acids, preferably selected from L-histidine, L-arginine, L-Lysine, L -ornithine and L-hydroxylysine. The light protection agent cells according to claim 1, characterized in that the ribonucleic acids are present in the form of their salts with basic peptides. The cell light-protecting agent according to any one of claims 1 to 5, characterized in that the above ribonucleotides are selected from the group of the conventional monoribonucleotides. The light protection cell according to claim 6, characterized in that the preferred ribonucleotides are the following: RIBONUCLEOTIDES AMP ADP ATP GMP GDP GTP CMP CDP CTP UMP UDP UTP IMP IDP ITP XMP XDP XTP The cell light-protecting agent according to claim 6 or 7, characterized in that the above ribonucleotides are present in the form of their salts with bases, enabling pH values of the order of 5.8 to 8 to be measured. which are biocompatible. The photoprotective cell according to claim 8, characterized in that the above ribonucleotides are present in the form of their salts with mineral bases, preferably selected from NaOH, KOH and NH4 or with organic bases, in particular triethanolamine. The photoprotective cell according to claim 8, characterized in that the above ribonucleotides are present in the form of their salts with basic proteins such as: - the histones or microproteins with a molecular weight between 11,000 and about 24,000, the globins or coupled proteins of hemoglobins and of myoglobins whose molecular weights are between about 15,000 and about 70,000. The photoprotective cell according to claim 8, characterized in that the above ribonucleotides are present in the form of their salts with basic amino acids, in particular one or more basic amino acids selected from the group consisting of L-histidine, L -arginine, L-lysine, L-ornithine and L-hydroxylysine. The photoprotective cell according to claim 8, characterized in that the above ribonucleotides are present in the form of their salts with basic peptides. The photoprotective cell according to claim 8, characterized in that the above ribonucleocides are selected from the group consisting of the conventional monoribonucleocides. The photoprotective cell according to claim 13, characterized in that the ribonucleocides are selected from: RIBONUCLEOSIDES. Adenosine. Cytidine. Guanosine. Inosine. uridine. Xanthosine The photoprotective cell according to any one of claims 1 to 4, characterized in that the nucleosides are combined or combined with one or more of said nucleoprotides or ribonucleotides or their salts in amounts calculated to obtain biocompatible PH values between 5.8 and 8. The light protection cell according to any one of claims 1-15, characterized in that it comprises derivatives of urocanic acid or urocanoprotides in the form of simple or complex salts of urocanic acid or derivatives of urocanic acid with certain proteins, peptides or amino acids. The photoprotective cell according to claim 16, characterized in that the derivatives of urocanic acid or urocanoprotides in the form of complex salts are preferably obtained by a combination of urocanic acid with: a. Basic proteins, advantageously histones or globins in particular the previously detained; b. light absorbing ribonucleotides such as AMP, ADP and ATP; c. basic peptides, d. basic amino acids preferably L-histidine, L-arginine, L-Lysine, L-hydroxylysine and L-o-rithithine individually or in combinations. The photoprotective cell according to claims 16-17, characterized in that the urocanic acid derivatives are complexes of urocanoprotides selected from the urocanohistones, urocanopeptides, basic urocanoamino acids and urocanonucleotides, which are more cytophilic than the derivatives or mineral alkali or alkaline earth metal salts. The light-protecting cell according to any one of claims 1-18, characterized in that it additionally contains amino acids and peptides or proteins. The photoprotective cell according to claim 19, characterized in that the above amino acids and peptides and proteins are selected from: 1. one or more of the 20 common amino acids of proteins listed below: Amino acids involved in the aforementioned complexes and combinations L-histidine, L-arginine, L-lysine, L-citrulline, L-ornithine and L-hydroxylysine. . Aromatic amino acids: L-tyrosine, L-phenylalanine, L-tryptophan. . Amino Dicarboxylic Acids: L-Glutamic Acid, L-Aspartic Acid. . Cyclic amino acids: L-proline * (L-hydroxyproline). . Aminomonocarboxylic acids: glycine, alanine, L-valine *, L-leucine *, L-isoleucine. . . Hydroxy amino acids: L-serine *, L-threonine *. . Amidated amino acids: L-glutamine *, L-asparagine. . Sulfur-containing amino acids and sulfur-containing oligo-peptides: L-cysteine *, L-methionine *, cystine *, * Epiderm amino acids which are abundant in keratin and have a light-protecting ability: 2. one or more of the usual cell peptides and proteins and / or peptides resulting from the acidic, basic or enzymatic hydrolysis of polypeptides such as glutathione and / or proteins, scleroproteins and soluble proteins such as:. Scleroproteins and their partial hydrolysates: For example: - silk fibroin concentrations of 1-10% - collagen concentrations of 1-10% - elastin concentrations of 1-10% - hydrophilic keratins Soluble proteins and their partial hydrolysates: For example: (in concentration of 0.1-10%) - histones - globins (hemoglobins and myoglobins) - plasma proteins (eg serum albumin and serum globulins) - partially hydrolysed (enzymatic pathway) plasma proteins, being blood plasma rich in proteins (approximately 8 %) and useful as a synergistic biological solvent for protection against light, biological transport. 21. Cosmetic or dermo-pharmaceutical preparation with the skin cells for light-protecting effect, in particular with activity against premature aging of the skin, in particular protective for the Langerhans cells, characterized in that it contains at least one of the cells against light-protecting agent as previously defined in any one of claims 1-20. Cosmetic or dermo-pharmaceutical preparation according to claim 21, characterized in that the concentration of the above-mentioned cells against light-protecting agents is similar to the concentration of the agents previously known for protecting the skin against light and is advantageously between 0, 01% and 10%, preferably 0.1 and 3% by weight, based on the total weight of the cosmetic or dermo-pharmaceutical preparation. Novel compounds characterized in that they are compounds selected from the group consisting of: A - the simple or complex salts of the aforementioned ribonucleic acids with organic bases selected from the groups consisting of basic proteins such as histone, globin, basic peptides or peptides such as glutathione; B - the aforementioned simple or complex salts of the ribonucleotides with organic bases selected from the groups consisting of the aforementioned basic proteins and basic peptides. Novel compounds according to claim 23, characterized in that the ribonucleotides are selected from: RIBONUCLEOTIDES AMP ADP ATP GMP GDP GTP CMP CDP CTP UMP UDP UTP IMP IDP ITP XMP XDP XT 25. A process for the preparation of a light-protecting agent for the skin cells, in particular with a specific light-protecting activity of the cells, in particular of the Langerhans cells, characterized in that at least one compound is active as the light-protecting component of the cells. as described in any one of claims 1-20. A method according to claim 25, characterized in that the salts of the ribonucleic acids with mineral or organic bases are prepared or, rather, the complex salts of the ribonucleic acids with basic proteins, basic amino acids or basic peptides as previously described. A method for preparing a skin-protecting cosmetic cell and / or dermo-pharmaceutical preparation with particular protective effect for the Langerhans cells, characterized in that at least one of the skin protecting cells is described as described previously in any one of claims 1-20, blends with a cosmetically and / or pharmaceutically compatible excipient or carrier.