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WO2008058999A1 - Composés innovants à base de dithiolane siliceux et leur utilisation - Google Patents

Composés innovants à base de dithiolane siliceux et leur utilisation Download PDF

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Publication number
WO2008058999A1
WO2008058999A1 PCT/EP2007/062343 EP2007062343W WO2008058999A1 WO 2008058999 A1 WO2008058999 A1 WO 2008058999A1 EP 2007062343 W EP2007062343 W EP 2007062343W WO 2008058999 A1 WO2008058999 A1 WO 2008058999A1
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WIPO (PCT)
Prior art keywords
radical
skin
dithiolan
methyl
preventing
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PCT/EP2007/062343
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English (en)
Inventor
Xavier Marat
Karine Lucet-Levannier
Marie-Jocelyne Pygmalion
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LOreal SA
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LOreal SA
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Priority claimed from FR0654960A external-priority patent/FR2908769B1/fr
Application filed by LOreal SA filed Critical LOreal SA
Publication of WO2008058999A1 publication Critical patent/WO2008058999A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/899—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing sulfur, e.g. sodium PG-propyldimethicone thiosulfate copolyol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/007—Preparations for dry skin

Definitions

  • the present invention relates to novel siliceous dithiolane-based compounds of formulae (I), (I') and (II) , to their use in compositions that are useful for treating or preventing disorders induced by oxidative stress, especially caused by sunlight, and to compositions containing them.
  • the skin is the outermost organ of our body and is thus the first target for environmental stress factors, most particularly represented by the ultraviolet radiation of sunlight, UVB and UVA. Specifically, acute or chronic exposure to sunlight is known to induce deleterious biological and clinical effects on the body.
  • UV-A or UV-B rays Cutaneous damage associated with chronic (repeated irradiation) or acute (strong irradiation) exposure to UV-A or UV-B rays has been extensively studied; it is especially known that : - UV-B rays (290-300 nm; 5% of the total UV range), which have the highest-energy wavelengths, above all affect the epidermal cells (keratinocytes) , by acting on DNA;
  • UV-A rays (320-400 nm; 95% of the total UV range), which are more penetrating, reach the dermal cells such as the fibroblasts and act indirectly via the generation of free radicals; furthermore, prolonged exposure to ultraviolet radiation has the effect of stimulating the expression of collagenases, particularly type-1 matrix metalloprotease (MMP-I) .
  • MMP-I type-1 matrix metalloprotease
  • UVB and UVA radiation induces various reactions, including direct and indirect induction of DNA lesions.
  • UV radiation for instance pyrimidine dimers and 6,4 photo products.
  • NER nucleotide excision repair
  • GER global excision repair GER
  • DNA lesions are also the cause of apoptosis processes inducing the formation of characteristic cells in the epidermis: the "sunburn cells”.
  • UV rays are responsible at the cellular level for the generation of reactive oxygen species, which are themselves the cause of many biological effects, for instance, the induction of oxidative damage to DNA (8-oxo guanine) or to numerous genes.
  • UV rays also have an impact on melanocytes (cells responsible for pigmentation) and the Langerhans cells, having an antigen-presenting immune function.
  • UV rays a direct action of UV rays on certain cellular chromophores such as DNA, but also by an indirect action.
  • AOS activated oxygen species
  • endogenous photo- sensitizers such as riboflavins, bilirubins, phaeomelanin and porphyrin derivatives.
  • AOSs Singlet oxygen and the superoxide anion undergo a cascade of reactions leading to the production of other AOSs, for instance hydrogen peroxide and hydroxyl radicals.
  • the AOSs thus generated damage DNA, cell membranes and certain proteins (enzymes, transcription factors, etc.).
  • Cells are equipped with an enzymatic antioxidant defence (superoxide dismutases Cu-Zn and Mn, catalases, glutathione peroxidases, etc.) and non-enzymatic defences (vitamins E and C, thiols, including glutathione, ⁇ -carotene, trace elements, etc.), whose role is to maintain the intracellular redox potential, but this defence capacity may be exceeded during an intense oxidative stress.
  • an enzymatic antioxidant defence superoxide dismutases Cu-Zn and Mn, catalases, glutathione peroxidases, etc.
  • non-enzymatic defences vitamins E and C, thiols, including glutathione, ⁇ -carotene, trace elements, etc.
  • Glutathione tripeptide ( ⁇ -L-glutamyl-L-cysteinyl- glycine or GSH) is the most ubiquitous and abundant of the non-protein low molecular weight thiols. The majority of the intracellular GSH exists in reduced form (GSH) . Glutathione disulfide (GSSG) represents less than 0.5% of the total GSH. In the majority of animal cells, the concentration of GSH is between 1 and 10 mM, whereas it is from about 0.5 to 10 ⁇ M in the plasma. The thiol function located on the cysteine residue gives it a redox potential (about -230 mV) that is predominant in metabolic redox phenomena.
  • a reduction in the level of glutathione will thus affect the cellular redox balance. It is especially known that exposure to UV leads to a depletion of the level of intracellular GSH, thus increasing the sensitivity of cells to oxidative stress.
  • the skin may be protected from the harmful effects of UV radiation by using sunscreens. These products contain molecules that absorb the harmful wavelengths before they reach the skin and damage it, thus preventing the acute and chronic effects of exposure to UV.
  • sunscreens do not have a global action. Since there are no screening agents that allow total absorption of the harmful wavelengths (UVB, UVA and long UVA) , a photoprotection strategy based on induction of the endogenous antioxidant defence systems offers advantageous perspectives.
  • Lipoic acid or thioctic acid (1, 2-dithiacyclopentane-3- valeric acid) is an endogenous dithiol widely found in plants and animals. It is a coenzyme for the metabolism of lipids and carbohydrates in mitochondrial multienzyme complexes such as pyruvate dehydrogenase and ⁇ -ketoglutarate dehydrogenase.
  • Lipoic acid also increases the cellular level of glutathione via regeneration of oxidized glutathione (GSSG) and increasing the activity of ⁇ -glutamylcysteine ligase (enzyme which controls GSH synthesis) .
  • A is a radical of formula (1) below:
  • L is a divalent radical for attaching the radical A to the silicone chain
  • m represents an integer 0, 1, 2, 3, 4, 5, 6, 7 or 8
  • - X represents an oxygen, nitrogen or sulfur atom
  • Y represents an oxygen or nitrogen atom, a group NR 4 or a sulfur atom
  • R 4 represents a hydrogen, a linear C1-C20, or branched C3-C20, saturated or unsaturated C2-C20 alkyl, optionally substituted with an optionally substituted phenyl radical,
  • R denotes a linear C1-C30 or branched C3-C20 saturated, or C2-C20 unsaturated hydrocarbon-based group, a halogenated C1-C8 hydrocarbon-based group or a trimethylsilyloxy group;
  • B which may be identical or different for the same compound, is chosen from the radicals R and A; r is an integer between 0 and 50 inclusive; s is an integer between 0 and 20 inclusive, and if s is 0, at least one of the two radicals B is A; u is an integer between 1 and 6 inclusive; t is an integer between 0 and 10 inclusive; it being understood that t + u is greater than or equal to 3.
  • L corresponds to either of the formulae (a) and (a' ) below:
  • Z is a linear or branched, saturated or unsaturated Ci-C ⁇ alkanediyl radical, optionally substituted with a hydroxyl or linear or branched, saturated or unsaturated C2-C8 alkyl radical;
  • Y' represents a hydrogen atom, a hydroxyl radical or a linear or branched, saturated or unsaturated Ci-Cs alkyl radical; p is 0 or 1.
  • the radicals R which may be identical or different, are chosen from linear Cl-ClO, or branched C3-C10, saturated or unsaturated alkyl radicals, the phenyl radical and the trifluoropropyl radical, at least 80% by number of the radicals R being a methyl radical .
  • 0 X represents an oxygen atom
  • 0 Y represents an oxygen or nitrogen atom
  • R 4 representing a hydrogen, a linear C1-C20 or branched C3-C20, saturated or unsaturated alkyl, optionally substituted with an optionally substituted phenyl radical;
  • 0 R is methyl
  • 0 B is methyl or a radical A; r is 0, 1, 2 or 3;
  • 0 s is 0, 1, 2 or 3;
  • 0 t + u is 3, 4 or 5.
  • 0 R is methyl
  • the invention also relates to the compounds of formula (H) :
  • ⁇ m represents an integer that may be 0, 1, 2, 3, 4, 5, 6, 7 or 8;
  • ⁇ X represents an oxygen, nitrogen or sulfur atom;
  • ⁇ Y represents an oxygen or nitrogen atom, a group NR 4 or a sulfur atom
  • ⁇ v represents an integer that may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;
  • ⁇ R 1 , R 2 and R 3 represent, independently of each other, a linear Cl-ClO or branched C3-C10, saturated or unsaturated alkyl radical, possibly comprising one or more halogen atoms (for example Cl, Br or F) , a phenyl radical or a benzyl radical;
  • ⁇ W is a linear C1-C8 or branched C3-C8, saturated or unsaturated alkyl radical, or C2-C8 alkylene radical, optionally substituted with a hydroxyl;
  • ⁇ R 4 represents a hydrogen, a linear C1-C20 or branched C3-C20, saturated or unsaturated alkyl, optionally substituted with an optionally substituted phenyl radical.
  • Y 0 or NR 4 ;
  • R 1 to R 3 denote linear C1-C4 or branched C3-C4 alkyl possibly comprising a phenyl radical, and more particularly methyl, ethyl, phenyl or -CH 2 -Ph;
  • ⁇ W is a methylene -CH 2 - or -CHOH-CH 2 - when v is other than 0;
  • D is -H or (CH 3 ) 3 .
  • R 1 to R 3 denote C1-C4 alkyl and more particularly methyl
  • 0 W is a methylene -CH 2 -.
  • the compounds according to the invention are :
  • This derivative is referred to hereinbelow as the "SiH derivative”.
  • the SiH groups may be present in the chain and/or at the chain ends. These SiH derivatives are products that are well known in the silicone industry and are generally commercially available. They are described, for example, in American patents US-A-3 220 972, US-A-3 697 473 and US-A-4 340 709.
  • SiH derivatives corresponding to the compounds of formulae (I) and (I') may thus be represented by formulae (2) to (4) below:
  • Ri, R2 and R3 have the meaning given above for formulae (II) ,
  • R, r, s, t and u have the meaning given above for formulae (I) and (I'),
  • B' which may be identical or different, are chosen from the radicals R and a hydrogen atom.
  • the hydrosilylation reaction is thus performed according to one of the following two reactions:
  • (I) and (II) consists in performing esterification reactions or ester, thioester or amide formation reactions from carboxylic acid or from derivatives that are synthetically compatible with the chosen route.
  • Hal represents a halogen atom and more particularly chlorine
  • M + represents an alkali metal and more particularly sodium or potassium.
  • Reagents that may be mentioned include hydroxymethyl- trimethylsilane (RN 3219-63-4), 2- (trimethyl- s i lyl ) ethanol ( RN 2 91 6- 68 - 9 ) and 3 - ( t rime thy 1 - s i lyl ) propanol ( RN 2 917 - 47 - 7 ) , which are commercial products .
  • Halosilane derivatives that may be mentioned include chloropropyltrimethylsilane (RN 2344-83-4) and chloro- methyltrimethylsilane (RN 2344-80-1) sold by the company Wacker.
  • iodomethyltrimethylsilane (RN 4206-67-1), (chloro- methyl)dimethylethylsilane (RN 3121-77-5), (chloro- methyl) dimethyl-n-butylsilane (RN 3121-75-3), (chloro- methyl) dimethylpentylsilane (RN 73013-39-5), (chloro- methyl) dodecyldimethylsilane (RN 70851-47-7), (chloro- methyl) triethylsilane (RN 757-34-6), 2-chloroethyl- trimethylsilane (RN 7787-87-3), bis (trimethyl- silyl)methylchloride (RN 5926-35-2), (chloro- methyl) dimethylphenylsilane (RN 1833-51-8), (chloro- methyl) diphenylmethylsilane (RN 18407-40-4) and (tri
  • the particularly preferred compounds of formulae (I), (I') and (II) may be advantageously obtained from lipoic acid.
  • the compounds according to the invention can prevent and/or correct this depletion of GSH, and can thus "boost" the endogenous antioxidant defence systems, in order to prepare the skin to better withstand a UV stress and to help it to repair itself.
  • Their activity was compared with a reference compound, lipoic acid, which is known for increasing the level of GSH.
  • the present invention also relates to the use of the compounds of general formulae (I), (I') and/or (II) as agents for stimulating the intracellular synthesis of glutathione and/or for maintaining an intracellular level of glutathione at an amount that is sufficient for preventing oxidative damage caused by free radicals on cells.
  • the use according to the invention can increase the cellular antioxidant defence systems, in particular the antioxidant defence systems of skin cells.
  • the skin cells are especially fibroblasts, keratinocytes, melanocytes, Langerhans cells, etc.
  • the compounds of general formulae (I), (I') and (II) are useful as skin photoprotective agents.
  • This use may be useful whether the skin has undergone exposure to daylight of an intensity lower than the minimum erythemal dose and whose effects do not produce visible signs on the skin, or whether the UV-ray damage is visible, for example by the appearance of redness on the skin.
  • the impairments range from simple discomfort such as a uniquely perceptible sensation of heating of the skin, to redness, or even irritation.
  • skin means the entire skin surface of the human body, including skin, mucous membranes and semi- mucous membranes, thus including the lips, the scalp, etc., and also the skin's appendages, especially the nails, bodily hair and head hair.
  • the compounds of general formulae (I), (I') and/or (II) are useful for preventing and/or treating UV stress and/or heating sensations caused by solar radiation, in particular UVA and/or UVB.
  • the compounds of general formulae (I), (I') and/or (II) are also useful for preparing a composition, comprising a physiologically acceptable medium, intended for preventing and/or treating skin impairments, such as skin redness and irritation, caused by solar radiation.
  • the compounds of general formulae (I), (I') and/or (II) are also useful for the preparation of a composition, comprising a physiologically acceptable medium, for preventing and/or treating DNA lesions caused by solar radiation and thus for preventing the development of cancers, in particular skin cancers.
  • a subject of the invention is also the use of at least one compound of formula (I), (I') or (II) for the preparation of a composition containing a physiologically acceptable medium, the said composition being intended for preventing and/or treating skin and/or mucous membrane disorders induced by irradiation with UVA and/or UVB radiation.
  • Solar irradiation or exposure is characterized by an exposure to sunlight, and may especially be an intense irradiation corresponding to exposure to zenithal sunlight or to solar radiation varying by an angle of 30° around this zenithal position and/or when the skin is subjected to UV radiation capable of inducing a solar erythema (redness commonly known as "sunburn”) , and defined by a minimum erythemal dose (MED) .
  • This dose varies as a function of the phototype of the individual and of the UVA/UVB ratio.
  • the invention is especially directed towards preventing or reducing damage induced in the skin, mucous membranes and/or the integuments of a mammal, in particular of a human being, by short exposure to erythemal doses of solar radiation.
  • These solar exposure conditions comprise UVA and/or UVB rays, at doses around the MED, in particular at a dose of greater than or equal to 1 MED.
  • the cosmetic use according to the invention of at least one compound of formulae (I), (I') and (II) in a composition containing a physiologically acceptable medium is particularly suitable for preparing the skin for exposure to sunlight.
  • a "physiologically acceptable medium” is either a cosmetically or pharmaceutically acceptable medium that is compatible with the skin, mucous membranes, the nails and/or the hair, or a medium that may be administered orally.
  • preparation of the skin for exposure to sunlight may be performed by the daily application to the skin of the said cosmetic composition for one week, and preferably two weeks, before the exposure to sunlight, just up to at least one day (between 6 and 18 hours) before the exposure to sunlight.
  • free radicals cause substantial oxidative damage, especially in cell membranes (lipid peroxidation causing degradation of the membrane permeability) , cell nuclei (destruction of DNA) and tissues, in particular connective tissue (degradation of elastin and collagen fibres, and depolymerization of polyuronic fibres) .
  • This damage especially leads to drying-out and loss of firmness and elasticity of the skin (Grinwald et al . 1980, Agren et al . 1997).
  • the compounds of general formulae (I), (I') and/or (II) according to the invention are useful as indirect antioxidant compounds for preventing and/or limiting the formation of free radicals and/or for removing the free radicals present in cells, and may be used for any skin disorder caused by oxidative stress .
  • the use of the compounds according to the invention allows the clinical signs of ageing to be prevented and/or treated.
  • Ageing is a natural physiological phenomena whose clinical signs are generally reflected on the skin by the appearance of wrinkles and fine lines, by slackening of the cutaneous and subcutaneous tissues, by a loss of skin elasticity and by atony of the texture of the skin.
  • the loss of firmness and tonicity of the skin, for instance wrinkles and fine lines, is at least partly accounted for by dermal atrophy and also flattening of the dermo-epidermal junction; the skin is less firm and more flaccid, and the thickness of the epidermis decreases.
  • the complexion of the skin is generally modified, and appears paler and yellowier. This phenomena appears to be due essentially to disorganization of the capillary circulation (less haemoglobin in the papillary dermis) .
  • Another clinical sign of ageing is the dry and coarse appearance of the skin, which is due essentially to greater desquamation; by diffracting light rays, these squamae also contribute towards the somewhat greyish appearance of the complexion.
  • numerous coloured and/or darker marks appear on the surface of the skin, and more especially on the hands, giving the skin heterogeneity. In general, these marks are due to a large production of melanin in the epidermis and/or the dermis of the skin.
  • diffuse irritation and occasionally telangiectasia may exist on certain areas of the skin.
  • Some of these signs are more particularly associated with intrinsic or physiological ageing, i.e. age- related ageing, whereas others are more specific to extrinsic ageing, i.e. ageing caused in general by the environment; this is more particularly a case of photo- ageing due to exposure to sunlight, light or any other radiation, or alternatively pollutants.
  • the subject of the invention is particularly suited towards the cosmetic use of at least one compound of general formulae (I), (I') and/or (II) according to the invention in a composition containing a physiologically acceptable medium, for preventing and/or treating loss of firmness and/or elasticity of the skin.
  • a use especially allows the skin to regain a uniformly smooth appearance.
  • Another subject of the invention is the cosmetic use of at least one compound of general formulae (I), (I') and/or (II) according to the invention in a composition containing a physiologically acceptable medium, for preventing and/or treating a dull complexion and/or for reviving the complexion.
  • the invention is also suited to the cosmetic use of at least one compound of general formulae (I), (I') and/or (II) according to the invention in a composition containing a physiologically acceptable medium, for preventing and/or treating skin dehydration.
  • the subject of the invention is also more generally suited to the cosmetic use of at least one compound of general formulae (I), (I') and/or (II) according to the invention in a composition containing a physiologically acceptable medium, for preventing and/or treating the signs of ageing of the skin.
  • the expression "signs of ageing of the skin” more particularly means pigmentation marks and/or hyperkeratosis marks and/or epidermal atrophy and/or skin roughness and/or skin dryness.
  • Another subject of the invention relates to the cosmetic use of at least one compound of general formulae (I), (I') and/or (II) in a composition containing a cosmetically acceptable medium, for preventing and/or treating the harmful effects of pollution on the skin.
  • the live cells which are in direct and permanent contact with the external environment (especially the skin, the scalp and certain mucous membranes) , are particularly sensitive to these effects of gaseous pollutants, which are especially reflected by accelerated ageing of the skin, with a complexion that lacks radiance, and an early formation of wrinkles or fine lines, and also by a decrease in the vigour and a dull appearance of the hair.
  • the subject of the invention is also useful for preventing and/or limiting and/or eliminating unpleasant body odour.
  • compositions according to the invention may be intended for cosmetic and/or dermatological use. They may be compositions suitable for topical application, in particular external topical application to the skin, mucous membranes and/or the integuments.
  • compositions according to the invention are suitable for the oral route, and are especially intended for oral cosmetic applications .
  • the amount of compound that may be used according to the invention obviously depends on the desired effect, and may thus vary within a wide range.
  • an extract as defined previously may be used topically in an amount representing from 0.001% to 20% of the total weight of the composition and preferentially in an amount representing from 0.01% to 10% of the total weight of the composition.
  • the composition according to the invention comprising at least one compound of formulae (I), (I') and/or (II) is constituted of a cosmetically acceptable medium, i.e. a medium that has a pleasant colour, odour and feel and that does not cause any unacceptable discomfort .
  • compositions are preferably cosmetic compositions or products.
  • Cosmetic product especially means any substance or preparation intended to be placed in contact with the various surface parts of the human body (epidermis, pilous and hair system, nails, lips and external genital organs) or with the teeth and the oral mucosae for the purpose, exclusively or mainly, for cleaning them, fragrancing them, modifying their appearance and/or correcting body odour and/or protecting them or keeping them in good condition (Amended Cosmetic Directive 76/768/EEC) .
  • composition according to the invention may especially be in the form of an alcoholic, aqueous- alcoholic or oily solution, a suspension, a dispersion, a W/O, O/W or multiple emulsion, aqueous or anhydrous gels, or a vesicular dispersion of ionic or nonionic type. It may have a liquid, semi-liquid, pasty or solid consistency.
  • the composition that may be used according to the invention may especially be in the form of an aqueous-alcoholic or oily solution or a dispersion of the lotion or serum type, emulsions of liquid or semi-liquid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous phase (O/W) or conversely (W/O) or multiple emulsions, a free or compacted powder to be used in unmodified form or to be incorporated into a physiologically acceptable medium, or suspensions or emulsions of soft consistency of the aqueous or anhydrous cream or gel type, or alternatively microcapsules or microparticles, or vesicular dispersions of ionic and/or nonionic type.
  • aqueous-alcoholic or oily solution or a dispersion of the lotion or serum type emulsions of liquid or semi-liquid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous phase (O/W) or conversely
  • It may thus be in the form of an ointment, a tincture, a cream, a pomade, a powder, a patch, an impregnated pad, a solution, an emulsion or vesicular dispersion, a lotion, a gel, a spray, a suspension, a shampoo, an aerosol or a mousse. It may be anhydrous or aqueous. It may also consist of solid preparations constituting soaps or cleansing bars.
  • compositions are prepared according to the usual methods .
  • the composition is suitable for oral use, in particular "cosmetic oral” use.
  • the composition may especially be in the form of wafer capsules, gel capsules, coated tablets, granules, plain tablets, chewable pastes, gels or drinkable syrups or in any other form known to those skilled in the art.
  • compositions that may be used according to the invention are those conventionally used in the fields under consideration.
  • compositions according to the invention may also contain agents for reinforcing or complementing the activity of the compound of formula (I), (I') or (II), and especially at least one compound chosen from antioxidants, antipollution agents, anti-UVA screening agents, anti-UVB screening agents, depigmenting agents and agents for stimulating DNA repair.
  • the compounds of formulae (I), (I') and (II) according to the invention may also be advantageously combined with extracts (total biomass, culture medium, ribosomal fraction, cell membrane fraction, LPS fraction, lipid A, etc.) of non-fruiting, non-photosynthetic filamentous bacteria such as Vitreoscilla filiformis or alternatively ⁇ 2- (acetyl (3-trifluoromethylphenyl) - amino] -3-methylbutyrylamino ⁇ acetic acid.
  • extracts total biomass, culture medium, ribosomal fraction, cell membrane fraction, LPS fraction, lipid A, etc.
  • non-photosynthetic filamentous bacteria such as Vitreoscilla filiformis or alternatively ⁇ 2- (acetyl (3-trifluoromethylphenyl) - amino] -3-methylbutyrylamino ⁇ acetic acid.
  • an antioxidant chosen from: vitamin E (tocopherol) and derivatives thereof, including the acetate, linoleate or nicotinate, preferably at concentrations of about from 0.1% to 5%, ⁇ -orizanol (0.1% to 5%) - lysine pidolate or arginine pidolate (0.5% to 10%), plant extracts such as extract of balm (0.01% to 2%), extract of silymarin (0.01% to 2%), extract of Ginkgo biloba (0.05% to 2%), extract of sage (0.05% to 2%), extract of cola nuts (0.05% to 2%), extract of rutin (0.1% to 2%) or extract of thyme (0.1% to 2%), the percentages being given as dry matter, carotenoids, such as ⁇ - and ⁇ -carotene or lycopene in a purified form or in an extract (for example tomato puree with a lycopene titre reaching a final
  • Eukarions including EUK-8, EUK-134 and EUK-189 developed by Proteome Systems
  • a mixture of several antioxidants may also be used.
  • free-radical scavengers in particular bioflavonoids; coenzyme QlO or ubiquinone; certain enzymes such as catalase, glutathione peroxidase and quinone reductases; glutathione; benzylidenecamphor; benzylcyclanones; substituted naphthalenones; pidolates; phytanetriol; lignans; melatonin; hydroxylated chalcones, and also reduced derivatives thereof.
  • bioflavonoids in particular bioflavonoids
  • coenzyme QlO or ubiquinone certain enzymes such as catalase, glutathione peroxidase and quinone reductases
  • glutathione glutathione
  • benzylidenecamphor benzylcyclanones
  • substituted naphthalenones pidolates
  • phytanetriol lignans
  • melatonin hydroxyl
  • the antioxidant is chosen from vitamin C, vitamin E, isopropyl (benzyl ⁇ 2- [benzyl (2-isopropoxy-2- oxoethyl) amino] ethyl ⁇ amino) acetate, ferulic acid, phloretin and SOD.
  • anti-pollution agent means any compound capable of trapping ozone, monocyclic or polycyclic aromatic compounds such as benzopyrene and/or heavy metals such as cobalt, mercury, cadmium and/or nickel.
  • free-radical scavenger means any compound capable of trapping free radicals.
  • vitamin C and its derivatives including ascorbyl glucoside; phenols and polyphenols, in particular tannins, ellagic acid and tannic acid; epigallocatechin and natural extracts containing it; extracts of olive tree leaf; extracts of tea, in particular of green tea; anthocyans; extracts of rosemary; phenol acids, in particular chorogenic acid; stilbenes, in particular resveratrol; sulfur-containing amino acid derivatives, in particular S-carboxy- methylcysteine; ergothioneine; N-acetylcysteine; chelating agents, for instance N, N' -bis (3, 4, 5-tri- methoxybenzyl) ethylenediamine or one of its salts, metal complexes or esters; carotenoids such as crocetin; and various starting materials, for instance the mixture of arginine, histidine ribonu
  • tannins such as ellagic acid
  • indole derivatives in particular 3-indolecarbinol
  • extracts of tea in particular of green tea, extracts of water hyacinth or Eichornia crassipes
  • water-soluble fraction of corn sold by the company Solabia under the trade name Phytovityl ® .
  • heavy-metal-trapping agents such as EDTA, the pentasodium salt of ethylenediaminetetramethylenephosphonic acid, and N, N'- bis (3, 4, 5-trimethoxybenzyl) ethylenediamine or one of the salts, metal complexes or esters thereof; phytic acid; chitosan derivatives; extracts of tea, in particular of green tea; tannins such as ellagic acid; sulfur-containing amino acids such as cysteine; extracts of water hyacinth (Eichornia crassipes) ; and the water-soluble fraction of corn sold by the company Solabia under the trade name Phytovityl ® .
  • chelating agents such as EDTA, the pentasodium salt of ethylenediaminetetramethylenephosphonic acid, and N, N'- bis (3, 4, 5-trimethoxybenzyl) ethylenediamine or one of the salts, metal complexes or esters thereof
  • phytic acid
  • compositions according to the invention contain at least one UVA-screening agent and/or at least one UVB-screening agent, preferably a combination of at least one UVA-screening agent and of at least one UVB-screening agent.
  • Sunscreens are molecules that absorb UV radiation and thus prevent it from reaching the skin cells. They can absorb either mainly UVB or mainly UVA, depending on their nature. There are two major categories of sunscreens, either organic, or mineral (zinc oxide or titanium oxide) . By using them in cosmetic compositions in combination and in a sufficient amount, they can block a large proportion of the UV radiation.
  • compositions in accordance with the invention may also comprise at least one organic photoprotective agent and/or at least one mineral photoprotective agent, which is (are) active in the UVA and/or UVB range (absorbers) , and which is (are) water-soluble or liposoluble, or even insoluble in the commonly used cosmetic solvents.
  • the additional organic screening agents are chosen especially from anthranilates; salicylic derivatives; camphor derivatives; benzophenone derivatives; ⁇ , ⁇ -diphenylacrylate derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives as described in patents EP 0 669 323 and US 2 463 264; p-aminobenzoic acid (PABA) derivatives; methylene- bis (hydroxyphenylbenzotriazole) derivatives as described in patent applications US 5 237 071, US 5 166 355, GB 2 303 549, DE 197 26 184 and EP 893 119; screening polymers and screening silicones such as those described especially in patent application WO 93/04665; dimers derived from ⁇ -alkyl- styrene, such as those described in patent application DE 198 55 649; 4, 4-diarylbutadienes such as those described in patent applications
  • Ethylhexyl dimethyl PABA sold in particular under the name Escalol 507 by ISP, Glyceryl PABA, PEG-25 PABA sold under the name Uvinul P25 by BASF.
  • TEA salicylate sold under the name Neo Heliopan TS by Haarmann & Reimer.
  • Benzylidenecamphor derivatives 3-Benzylidenecamphor manufactured under the name Mexoryl SD by Chimex,
  • Phenylbenzimidazolesulfonic acid sold especially under the trade name Eusolex 232 by Merck,
  • Disodium phenyldibenzimidazoletetrasulfonate sold under the trade name Neo Heliopan AP by Haarmann & Reimer.
  • Phenylbenzotriazole derivatives Drometrizole trisiloxane sold under the name Silatrizole by Rhodia Chimie, methylenebis (benzotriazolyl) tetramethylbutylphenol sold in solid form under the trade name MIXXIM BB/100 by Fairmount Chemical, or in micronized form as an aqueous dispersion under the trade name Tinosorb M by Ciba Specialty Chemicals.
  • Neo Heliopan MA Menthyl anthranilate sold under the trade name Neo Heliopan MA by Haarmann & Reimer.
  • Imidazoline derivatives Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate .
  • Benzalmalonate derivatives Polyorganosiloxane containing benzalmalonate functions, for instance Polysilicone-15, sold under the trade name Parsol SLX by Hoffmann LaRoche.
  • the preferential organic UV-screening agents present in the compositions are chosen from: Ethylhexyl salicylate,
  • the additional mineral photoprotective agents are chosen from pigments and even more preferentially nanopigments (mean size of the primary particles: generally between 5 nm and 100 nm and preferably between 10 nm and 50 nm) of treated or untreated metal oxides such as, for example, nanopigments of titanium oxide (amorphous or crystallized in rutile and/or anatase form) , or of iron oxide, zinc oxide, zirconium oxide or cerium oxide.
  • the treated nanopigments are pigments that have undergone one or more surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal (titanium or aluminium) alkoxides, polyethylene, silicones, proteins (collagen or elastin) , alkanolamines, silicon oxides, metal oxides, sodium hexametaphosphate, alumina or glycerol.
  • surface treatments of chemical, electronic, mechanochemical and/or mechanical nature with compounds as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64 such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfact
  • the treated nanopigments may more particularly be titanium oxides treated with: silica and alumina, such as the products Micro- titanium Dioxide MT 500 SA and Microtitanium dioxide MT 100 SA from the company Tayca, and the products Tioveil Fin, Tioveil OP, Tioveil MOTG and Tioveil IPM from the company Tioxide, alumina and aluminium stearate, such as the product Microtitanium Dioxide MT 100 T from the company Tayca, - alumina and aluminium laurate, such as the product Microtitanium Dioxide MT 100 S from the company Tayca, iron oxides and iron stearate, such as the product Microtitanium Dioxide MT 100 F from the company Tayca, silica, alumina and silicone, such as the products Microtitanium Dioxide MT 100 SAS, Microtitanium Dioxide MT 600 SAS and Microtitanium Dioxide MT 500 SAS from the company Tayca, -
  • titanium oxide nanopigments treated with a silicone are preferably Ti ⁇ 2 treated with octyltrimethylsilane and for which the mean size of the elementary particles is between 25 and 40 nm, such as the product sold under the trade name T 805 by the company Degussa Silices, Ti ⁇ 2 treated with a polydimethylsiloxane and for which the mean size of the elementary particles is 21 nm, such as the product sold under the trade name 70250 Cardre UF TiO2SI3 by the company Cardre, anatase/rutile Ti ⁇ 2 treated with a polydimethylhydrogenosiloxane and for which the mean size of the elementary particles is 25 nm, such as the product sold under the trade name Microtitanium Dioxide USP Grade Hydrophobic by the company Color Techniques.
  • the uncoated titanium oxide nanopigments are sold, for example, by the company Tayca under the trade names Microtitanium Dioxide MT 500 B or Microtitanium Dioxide MT 600 B, by the company Degussa under the name P 25, by the company Wackher under the name Oxyde de titane transparent PW, by the company Miyoshi Kasei under the name UFTR, by the company Tomen under the name ITS and by the company Tioxide under the name Tioveil AQ.
  • the uncoated zinc oxide nanopigments are, for example: those sold under the name Z-Cote by the company
  • the coated zinc oxide nanopigments are, for example: - those sold under the name Zinc Oxide CS-5 by the company Toshibi (ZnO coated with polymethylhydrogenosiloxane) ; those sold under the name Nanogard Zinc Oxide FN by the company Nanophase Technologies (as a 40% dispersion in Finsolv TN, C12-C15 alkyl benzoate) ; those sold under the name Daitopersion ZN-30 and Daitopersion ZN-50 by the company Daito (dispersions in cyclopolymethylsiloxane/oxyethylenated polydimethylsiloxane, containing 30% or 50% of nanozinc oxides coated with silica and polymethylhydrogenosiloxane) ; those sold under the name NFD Ultrafine ZnO by the company Daikin (ZnO coated with perfluoroalkyl phosphate and copolymer based on perfluoroalkylethyl as a dispersion in cyclopent
  • the uncoated iron oxide nanopigments are sold, for example, by the company Arnaud under the names Nanogard WCD 2002 (FE 45B) and Nanogard Iron FE 45 BL AQ, Nanogard FE 45R AQ, Nanogard WCD 2006 (FE 45R) or by the company Mitsubishi under the name TY-220.
  • the coated iron oxide nanopigments are sold, for example, by the company Arnaud under the names Nanogard WCD 2008 (FE 45B FN), Nanogard WCD 2009 (FE 45B 556), Nanogard FE 45 BL 345 and Nanogard FE 45 BL or by the company BASF under the name Transparent Iron Oxide.
  • metal oxides especially of titanium dioxide and of cerium dioxide, including the silica-coated equal-weight mixture of titanium dioxide and of cerium dioxide, sold by the company Ikeda under the name Sunveil A, and also the alumina, silica and silicone-coated mixture of titanium dioxide and of zinc dioxide, such as the product M 261 sold by the company Kemira, or the alumina, silica and glycerol-coated mixture of titanium dioxide and
  • the nanopigments may be introduced into the particles according to the invention in unmodified form or in the form of pigmentary paste, i.e. as a mixture with a dispersant, as described, for example, in document GB-A-2 206 339.
  • the additional photoprotective agents are generally present in the compositions according to the invention in proportions ranging from 0.01% to 20% by weight relative to the total weight of the composition, and preferably ranging from 0.1% to 10% by weight relative to the total weight of the composition.
  • depigmenting or antipigmenting agents that may be incorporated into the composition according to the invention comprise, for example, the following compounds: kojic acid; ellagic acid, arbutin and derivatives thereof such as those described in patent applications EP-895 779 and EP-524 109; hydroquinone; aminophenol derivatives such as those described in patent applications WO 99/10318 and WO 99/32077, and in particular N-cholsteryloxycarbonyl-para-aminophenol and N-ethyloxycarbonyl-para-aminophenol; iminophenol derivatives, in particular those described in patent application WO 99/22707; L-2-oxothiazolidine-4- carboxylic acid or procysteine, and also the salts and esters thereof; calcium D-pantethinesulfonate, ascorbic acid and derivatives thereof, especially ascorbyl glucoside; and extracts of plants, in particular of liquorice, of mulberry, of skullcap and of Bacopa monnieri, without this list
  • a vitamin E derivative that may be used is especially tocopheryl acetate.
  • the agents for stimulating DNA repair are especially agents that promote its repair, such as photolyase and/or endonuclease T4.
  • composition may also contain moisturizers, NO- synthase inhibitors, free-radical scavengers or agents for stimulating the synthesis of epidermal macromolecules and/or for preventing their degradation.
  • the organic phase is washed with water, with saturated sodium hydrogen carbonate solution and with saturated sodium chloride solution.
  • the organic phase is washed with water and then with saturated sodium chloride solution.
  • 0.2 ml (1.5 mmol) of 1-chloro-N, N-2-trimethylpropenyl- amine are added dropwise to a solution of 0.3 g (1.5 mmol) of 5- (1, 2-dithiolan-3-yl) pentanoic acid in 10 ml of anhydrous tetrahydrofuran in a dry 50 ml two- necked flask under argon.
  • the reaction medium is stirred for one hour at room temperature, and a mixture of 0.3 ml (2.25 mmol) of aminomethyltrimethylsilane and 0.3 ml (2.25 mmol) of triethylamine is then added dropwise.
  • Example 5 Measurement of the activity towards increasing the level of GSH of the compounds according to the invention
  • the study consisted in evaluating at the cellular level the protective effect of the reference molecule, lipoic acid, and also of the lipoic acid derivatives according to the invention, towards the UVD-induced depletion of intracellular GSH.
  • the UVD corresponds to the radiation of non-zenithal sunlight and to an average spectral illumination: it stimulates the radiation received by the skin of an individual in the course of a day and not solely to that corresponding to exposure to zenithal sunlight.
  • Devices for reproducing this radiation are described in FR 2 863 356.
  • the evaluation technique uses a fluorescent probe, monochlorobimane (MCB) .
  • MCB has the particular feature of having, unlike other bimane compounds such as monobromobimane, more selective reactivity towards glutathione: the blue fluorescent compound measured
  • GSH-monochlorobimane results from an enzymatic reaction catalysed by glutathione-S-transferase .
  • the specificity of MCB towards GSH in our keratinocyte model (HaCaT line) was confirmed previously.
  • the protection afforded by these two active agents against the depletion of GSH induced by the daily UV is higher than that of the reference molecule, lipoic acid (cf.
  • Example 6 Measurement of the protection afforded against DNA damage Solar UV is capable of giving rise to extensive oxidative damage in skin cells, and especially in DNA.
  • the nucleic acids absorb the UVB photons, thus inducing DNA damage directly.
  • UVA is not directly absorbed by DNA, it has a genotoxic action mediated by reactive oxygen species.
  • UVA UV- induced DNA damage
  • the principle of this test is based on the capacity of denatured and cleaved DNA fragments to migrate outside the cell nuclei, under the influence of an electric field, whereas undamaged DNA remains confined in the nucleus.
  • the damaged DNA fragments form a trail behind the nucleus of the cells.
  • the cells then take the appearance of "comets".
  • the "tail" of each comet is proportionately larger and stronger the greater the DNA damage incurred. (Alapetite C. et al . , 1996, Int. J. Rad. Bio.; Klaude M, et al . , 1996, Mut . Res.; Lehmann J. et al., 1998, Mut. Res.; Singh NP. et al . , 1988, Exp. Cell Res. ) .
  • Example 2-2 with respect to UVA-induced DNA damage.
  • normal human fibroblasts were placed in contact with the active agents for 24 hours. The cells were then detached, included in an agarose gel and then deposited on a microscope slide. Following the UVA exposure (for 30 minutes) , the cells were subjected to a cell lysis (so as to keep intact only the genetic material) , to a DNA-denaturing step and then to an electrophoresis to make the damaged DNA migrate. The level of damaged DNA was measured using a fluorescence microscope combined with specialized image analysis software.
  • Example 7 Formulations Antisun composition (oil-in-water emulsion)
  • the fatty phase containing the compound is heated at about 70 - 80 0 C until completely melted.
  • the water is then added in a single portion at 80 0 C with vigorous stirring. Stirring is continued for 10 to 15 minutes, the mixture is then allowed to cool with moderate stirring to about 40 0 C and the preserving agents are added.
  • Antisun composition oil-in-water emulsion
  • This cream is prepared according to the standard techniques for preparing emulsions by dissolving the screening agent in the fatty phase containing the emulsifiers, heating this fatty phase to 70-80 0 C and adding, with vigorous stirring, the water heated to the same temperature. Stirring is continued for 10 to 15 minutes and the mixture is then allowed to cool with moderate stirring, and the fragrance and preserving agent are finally added at about 40 0 C.

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Abstract

La présente invention concerne des composés innovants à base de dithiolane siliceux répondant aux formules (I), (I') et (II), leur utilisation dans des buts thérapeutiques ou cosmétiques, spécialement en tant qu'agents protecteurs contre le stress oxydatif, en particulier pour la photo-protection de la peau. L'invention concerne également des compositions cosmétiques ou dermatologiques qui les contiennent.
PCT/EP2007/062343 2006-11-17 2007-11-14 Composés innovants à base de dithiolane siliceux et leur utilisation Ceased WO2008058999A1 (fr)

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FR0654960 2006-11-17
FR0654960A FR2908769B1 (fr) 2006-11-17 2006-11-17 Nouveaux composes derives dithiolanes silicies et leur utilisation
US87061806P 2006-12-19 2006-12-19
US60/870,618 2006-12-19

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2936153A1 (fr) * 2008-09-24 2010-03-26 Oreal Utilisations de composes dithiolanes pour la photoprotection de la peau ; nouveaux composes dithiolanes ; compositions les contenant.
FR2936146A1 (fr) * 2008-09-24 2010-03-26 Oreal Utilisations de composes dithiolanes pour la photoprotection de la peau ; nouveaux composes dithiolanes ; compositions les contenant.
WO2010040603A1 (fr) * 2008-10-10 2010-04-15 L'oreal Composés de dithiolane ; compositions les contenant, leurs utilisations pour la photoprotection de la peau
US9421180B2 (en) 2011-09-30 2016-08-23 Perio Sciences, Llc Antioxidant compositions for treatment of inflammation or oxidative damage

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US20040161435A1 (en) * 2003-02-14 2004-08-19 Gupta Shyam K. Skin Firming Anti-Aging Cosmetic Mask Compositions

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US20040161435A1 (en) * 2003-02-14 2004-08-19 Gupta Shyam K. Skin Firming Anti-Aging Cosmetic Mask Compositions

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2936153A1 (fr) * 2008-09-24 2010-03-26 Oreal Utilisations de composes dithiolanes pour la photoprotection de la peau ; nouveaux composes dithiolanes ; compositions les contenant.
FR2936146A1 (fr) * 2008-09-24 2010-03-26 Oreal Utilisations de composes dithiolanes pour la photoprotection de la peau ; nouveaux composes dithiolanes ; compositions les contenant.
EP2168567A1 (fr) 2008-09-24 2010-03-31 L'Oréal Utilisations de composés dithiolanes pour la photoprotection de la peau, composés dithiolanes et compositions les contenant
JP2010077121A (ja) * 2008-09-24 2010-04-08 L'oreal Sa 皮膚を光保護するためのジチオラン化合物の使用、新規ジチオラン化合物、それを含有する組成物
US8530511B2 (en) 2008-09-24 2013-09-10 L'oreal Administration of dithiolane compounds for photoprotecting the skin
JP2015127348A (ja) * 2008-09-24 2015-07-09 ロレアル 皮膚を光保護するためのジチオラン化合物の使用、新規ジチオラン化合物、それを含有する組成物
CN101683311B (zh) * 2008-09-24 2016-04-20 莱雅公司 二硫戊环化合物用于皮肤光防护的用途；新型二硫戊环化合物；含有它们的组合物
WO2010040603A1 (fr) * 2008-10-10 2010-04-15 L'oreal Composés de dithiolane ; compositions les contenant, leurs utilisations pour la photoprotection de la peau
FR2937035A1 (fr) * 2008-10-10 2010-04-16 Oreal Composes dithiolanes ; compositions les contenant ; utilisations pour la photoprotection de la peau
US9421180B2 (en) 2011-09-30 2016-08-23 Perio Sciences, Llc Antioxidant compositions for treatment of inflammation or oxidative damage
US10918613B2 (en) 2011-09-30 2021-02-16 Perio Sciences, Llc Antioxidant compositions for treatment of inflammation or oxidative damage

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