Oligopeptides in Sensory, Proteins in Winter Skin and Carotenoids: Literature Findings

This month’s survey of recent patent and literature research describes money-making ideas in the personal care industry, ranging from oligopeptides for sensory properties and peptides for hair, to a dandruff treatment and colorless carotenoids for sun damage protection.

Skin and Skin Care
Oligopeptides in sensory: Evonik Goldschmidt discloses oligopeptide-containing dermatological compositions for increasing sensory detection in skin.1 The described compositions contain oligopeptides 4, 5 or 6; amino acids; and the dipeptide sequences Ile-Pro and/or Pro-Ile. The oligopeptides can be acylated or biotinylated. An example is shown in Formula 1.

Correcting aging, ischemic cell metabolism: Sephar describes a new pharmaceutical and cosmetic composition and its applications in correcting the metabolic activity of aging and ischemic cells.2 The composition, referred to as Cell Restructuring Complex 50 (CRC-50), contains methylsilanol mannuronate, serum albumin from soybean extract, triterpene saponosides from Centella asiatica extract, gamma-oryzanol, alpha-tocopherol, caffeine, zinc gluconate, flavonoids such as the escin from Aesculus hippocastanum extract, and ammonium glycyrrhizinate. The effects of this composition on collagen production and stimulation of cultured fibroblasts were shown.

Aniline, o-toluidine penetration: Korinth et al. have published on the enhancement of percutaneous penetration of aniline and o-toluidine in vitro using skin barrier creams.3 During the production and processing of rubber, aniline (ANI) and the human carcinogen o-toluidine (OT) are released. Recently, these investigators showed that in rubber industry workers, frequent use of skin barrier creams increased their internal exposure of ANI and OT.

In the present study, diffusion cells were used to investigate the effects of three creams on percutaneous penetration of ANI and OT: two skin barrier creams designed to protect skin, and one skin care cream without protectants. In addition, the penetration of OT from a mixture with a workplace-specific lubricant also was studied. The experiments were conducted on human skin that was either treated with skin cream or untreated. A considerable percutaneous penetration enhancement of test compounds was observed for the treated skin, as compared with the untreated skin; the greatest penetration enhancement was noted with an o/w emulsion-based skin barrier cream. The lowest penetration enhancement was observed with the skin care cream-treated skin. The in vitro data supported the findings that the percutaneous absorption of aromatic amines significantly increased in workers who used skin creams. The efficacy of skin creams to protect the percutaneous penetration of aromatic amines was not confirmed by these studies.

Alpha-arbutin glycosylation for industrial production, applied in skin lightening: Sugimoto et al. reviewed the development of alpha-arbutin production on an industrial scale, and its application as a skin-lightening cosmetic ingredient.4 The investigators discovered a new enzyme that was shown to efficiently catalyze transglycosylation reaction toward phenolic hydroxyl groups. This enzyme, hydroquinone glucosylating enzyme, catalyzed selective glycosylation of hydroquinone, and the yield of the resulting product, 4-hydroxyphenyl-O-alpha-d-glucopyranoside (alpha-arbutin), reportedly was high enough for industrial production.

Kojic acid, caffeic acid and many other phenolic compounds also were glycosylated by the reaction of this enzyme; however, alcohols were not. Application studies of alpha-arbutin were carried out and indicated that the material strongly inhibited human tyrosinase. Researchers also noted that its inhibitory effect on human tyrosinase was much higher than that of its isomer, 4-hydroxyphenyl-O-beta-d-glucopyranoside (arbutin).

Glycosides of alpha-arbutin and arbutin were then synthesized and their inhibitory effects compared; human tyrosinase indicated that the molecular size and electrostatic potential around the benzene ring are important for inducing the inhibitory effect of hydroquinone glycosides toward human tyrosinase. Further, the inhibitory effects of alpha-arbutin on melanin biosynthesis were examined. Alpha-arbutin was found to inhibit melanin syntheses of HMV-II cells and the human skin model in a dose-dependent manner, and at a noncytotoxic concentration. These results demonstrate that alpha-arbutin is an effective and safe ingredient for skin lightening.

Skin lipid review: Bouwstra et al. review skin lipid organization, composition and barrier function.5 As is generally known, the primary function of skin is to act as a barrier against unwanted influences from the environment and to protect the body from water loss. This barrier function is located in the superficial layer of the skin, the stratum corneum (SC). The SC consists of dead cells filled with keratin and water-the corneocytes-embedded in lipid regions. The lipid regions are the only continuous structure in the SC and thus are considered key to the skin barrier function.

The main lipid classes are ceramides, cholesterol, and free fatty acids. In this review paper, the authors examined lipid organization in human SC and the role the various classes play in lipid organization by studying mixtures prepared either from native human ceramides or synthetic ceramides. Finally, the paper describes a model to study the relationships between lipid composition, organization and barrier function. This model is referred to as the SC substitute.

Carbonyl protein levels in winter skin: Kobayashi et al. have reported on increased carbonyl protein levels during winter in the SC of the face.6 The SC is the interface between the body and the environment and is continuously exposed to oxidative stress that results in carbonyl modification of proteins. The investigators had previously developed a simple and noninvasive method to assess SC carbonyl protein (SCCP) levels. In the present study, they used this method to examine the seasonal changes in the SCCP levels and the relationship between the SCCP level and the physiological condition of the SC.

SC was collected from the faces of only healthy Japanese volunteers by adhesive tape stripping, and its carbonyl groups were determined by reaction with fluorescein-5-thiosemicarbazide. The average fluorescence intensity of the SC was calculated as the SCCP level, and this level was found to be higher in winter than in summer. The SCCP level was negatively correlated with the water content in the SC, measured by the conductance and capacitance, and also negatively correlated with the extensibility of the skin, measured by a cutometer. This suggests that the mechanical properties of the skin can be affected by oxidative modification of the SC. The data suggests the involvement of oxidative modification of SC proteins in the generation of rough skin during winter.

Protein carbonylation and optical properties of the SC: Iwai et al. have published on in vitro changes in the optical properties of the SC, induced by protein carbonylation.7 The skin is the frontier against the external environment and is continuously exposed to environmental oxidative stress such as UV irradiation. Protein carbonyls are the major oxidative products of protein and may be introduced by their reaction with aldehydes derived from lipid peroxide. Acrolein is one of the most reactive aldehydes generated during degradation of lipid peroxides, and protein-acrolein adducts have been found in oxidatively damaged lesions in UV-damaged skin.

Recent studies revealed that protein carbonyls also are detected in the thin outermost layer of the SC. However, the effect of protein carbonylation on the function of SC was unclear. In the described study, researchers treated SC sheets of reconstructed human epidermis and porcine epidermis with acrolein to explore the influence of protein carbonylation on the SC.

Human and porcine SC sheets treated with acrolein showed less transmission at visible light than the untreated SC sheets. Attenuated total reflection-IR spectroscopy with curve fitting analysis of amide I region showed that acrolein induced alterations in protein secondary structure of the porcine SC sheets, which were accompanied by a diminished fibrous keratin structure observed by transmission electron microscopy. These results suggest that carbonylation of the SC caused by environmental influences is one of the factors that alters the fibrous structure of keratin and decreases the light transmission of SC, which changes the quality of the skin’s appearance.

Hair and Hair Care
Raw materials for hair repair: Ikeda et al. review the properties of functional raw materials for hair care.8 In the described study, the authors evaluated three raw materials for their ability to rapidly repair damaged hair. A polymer blenda of butyl acrylate/isopropyl acrylamide/PEG-18 dimethacrylate crosspolymer was composed of thermo-responsive, highly-polymerized compounds and hydrophilic, highly-polymerized compounds.

The aqueous solution of this polymer becomes a hydro-gel that forms a sol-gel change at high temperatures. At a transition point, the thermo-responsive, highly-polymerized compound becomes a hydrophobic molecule and produces a hydrophobic film at low concentrations. Researchers found that this hydrophobic film controlled hair moisture content.

Also, liquefied shea was confirmed to absorb UV rays and can be used in hair care formulations to protect hair. Finally, hematinb was combined with the side chain of cysteine and histidine on the surface of the hair and found to repair damaged hair. It additionally was found to assist in maintaining permanent waves by holding moisture in hair.

Mild oxidation coloring: Doering et al. have published on super mild oxidation coloring and preventing hair damage at the molecular level.9 Hydrogen peroxide is widely used for oxidation hair coloring or bleaching. It displays a high redox potential and easily penetrates into the hair fiber. This renders hydrogen peroxide capable of nonspecific interactions with cortex and cuticle proteins, resulting in irreversible cleavage of cystine cross-links.

In the present work, various classes of antioxidants were screened for anti-damage effects in a permanent hair dye formulation using NIR spectroscopy. In parallel, the effect of coloring and lightening performance was studied to exclude unwanted side effects on primary product performance. The screening criteria were fulfilled by organic disulfides such as alpha-lipoic acid but interestingly not by antioxidants such as tocopherol, dibutylhydroxytoluene or beta-carotene.

Alpha-lipoic acid significantly protected human hair during oxidation coloring, as demonstrated by amino acid and protein analysis; surface polarity measurement; lipid analysis; differential scanning calorimetry; and combing work measurements. The results showed that radical scavenging properties alone do not render antioxidants suitable for hair protection during oxidative treatments. The presence of disulfide bonds appeared to be favorable, and it is likely that the intramolecular cross-linking within alpha-lipoic acid provided a kinetically controlled protection for cystine cross-linking during oxidation coloring.

Two-phase curl retention system: KPSS-Kao Professional Salon Services has disclosed a two-phase composition for conditioning and improving curl retention in permanently shaped and/or natural curly hair.10 The described invention comprises two optically separated phases at a zero shear rate that become homogeneous upon shaking and return to optically separated phases. Specifically, the invention includes a 5.0% to 50% w/w oil phase and a 50% to 95% w/w aqueous phase wherein the oil phase comprises: at least one volatile oil, at least one fixing polymer, at least one water miscible organic solvent and 0.05% to 2.0% of a cationic surfactant. The oil phase also contains trisiloxane and fragrance, and the aqueous phase contains vinyl acetate-vinylpyrrolidone copolymer, steartrimonium chloride, di-C12-15-alkyldimonium chloride, ethanol, citric acid/ammonium hydroxide and water.

Raw Materials
Oleyl sarcosine for thickening, deposition: Guala et al. have presented a new view on oleoyl sarcosine and review its applications.11 Acyl sarcosinates have been known for their foaming ability, skin mildness and compatibility with many surfactants and conditioning agents. In particular, oleoyl sarcosine has been widely used as a corrosion inhibitor and leather treatment. In this work, the authors explore its possible applications in cosmetics—a completely new field. The authors demonstrate that oleoyl sarcosine can be used as an effective thickening agent for surfactant solutions and to increase emollient deposition on the skin. Applications in cosmetics also are described.

Amino acid, peptide derivatives for hair care: Daikai reviews the development and application of a novel amino acid derivative and a novel peptide derivative for hair care.12 Hair conditioning agents are expected to absorb on or into hair to enhance its attributes. Here, the author has developed two novel hair care ingredients: an amino acid based on a low molecular amphoteric moisturizer, and a peptide-derived silicone polymer. These materials have been shown to regenerate properties of healthy hair in damaged hair, which was achieved by introducing a glycerol moiety into the arginine molecule. This novel moisturizer is reported to adsorb onto the cuticle edge of the hair surface and into the hair, raising the moisture content and thus increasing the tensile strength of the hair treated. As a result, water evaporation from inner hair is reduced and decolorization is prevented after coloring treatment.

Hair regeneration, methylacrylate copolymers in hair cosmetics: Daito Chemical Industry Co. discloses hair-repairing agents and hair cosmetics containing methacrylate copolymers.13 The disclosed repair agents are polyfluorooctyl methacrylate; N,N-diethylaminoethyl methacrylate; 2-hydroxyethyl methacrylate; and 2,2’-ethylenedioxydiethyl dimethacrylate copolymer (I) and/or its salts. The hair cosmetics described contain these agents, preferably at 0.1% to 5.0% w/w, and may also contain silicone gum. These agents were found to be effective at repairing damaged hair.

Orcein for hair coloring: L’Oréal disclosed the use of orcein for coloring human hair.14 A hair dye was described comprising orcein and at least a surfactant and/or a thickening polymer, including: 5% benzyl alcohol, 15% ethanol, 0.2% benzoic acid, 1.6% hydroxyethyl cellulose, and 0.5% alpha-hydroxy-orcein. This formula was applied to white hair; the hair was rinsed, shampooed, washed and dried; and a dark purple was obtained.

Styrylic or iminic dye and zinc salt in hair dye: L’Oréal also described a method for dyeing hair by means of a styrylic or iminic dye, in combination with a zinc salt.15 This invention relates to a process for dyeing human keratin fibers, such as hair, using a dye composition comprising at least one dye of styryl or imine type in the presence of a revealing composition comprising a zinc salt.

The invention also relates to a device suitable for implementing said process. The invention is reported to provide chromatic and fast coloration of keratin fibers that is visible even on dark hair that has not had any previous lightening treatment. It also provides coloration that under certain conditions does not stain. An example is shown in Formula 2.

C10-14 alkanediols for dandruff: Symrise GmbH discloses the use of C10-14 alkanediols in a composition for the prophylaxis and/or treatment of malassezia-induced dandruff formation.16 This invention uses C10-14 alkane-1,2-diols—in particular 1,2-decanediol, 1,2-dodecanediol and/or 1,2-tetradecanediol. An example antidandruff shampoo is shown in Formula 3.

Formulation variations and their impact on sprayable sunscreens: Durand et al.17 have studied the possible influence of different formulation and technological parameters—such as sunscreen type and concentration, viscosity, propellant gas, actuator and valve type—on size and size distribution of droplets in waterproof sunscreen emulsions conditioned in aerosol cans. W/Si and w/o emulsions were prepared with high concentrations of organic and inorganic UV filters. These formulations were incorporated in aerosol cans with a blend of butane, propane and isobutane.

The size and size distribution of the droplets were analyzed by laser diffraction. The results showed that the sprayability of the formulation and the particle size characteristics of the emitted sprays are dependent on the physicochemical properties of the formulations. Sprayable waterproof sunscreen emulsions with a high SPF and negligible percentage of emitted droplets, below 30 mm, were successfully developed by optimizing formulation parameters and using appropriate actuators and valves.

Colorless carotenoids for UV protection inside and out: von Oppen-Bezalel has published on UVA protection from the inside and outside with the colorless carotenoids phytoene and phytofluene.18 UVA causes damage by triggering an array of molecules in the cell to break down, resulting in the production of free radicals and reactive oxygen species (ROS). These potent mutagenic agents can cause changes in the physical structure of DNA.

Phytoene and phytofluene have been shown to effectively quench hydroxyl radicals and thus are effective against UVB/UVA damage. These materials were shown to protect DNA from damage caused by hydroxyl radicals by their ability to inhibit MMP-1 expression in IL-1 induced normal human fibroblasts in vivo, as well as their capability to inhibit melanin synthesis under UV-induced conditions. In addition, phytofluene lessened the energy of the light source from short, harmful wavelengths to longer, less-damaging wavelengths while zeta-carotene had significant absorption at the longer (higher) UVA wavelengths. Thus, phytoene and phytofluene, colorless carotenoids, could lessen the downstream effect of the UV light of collagen degradation to keep skin looking youthful.

Send e-mail to [email protected].
1. DE 102,006,047,529, Oligopeptides containing dermatological compositions for increase of skin sensing properties and sensory threshold, Evonik Goldschmidt GmbH, Germany (Apr 10, 2008)
2. FR 2,906,723, New pharmaceutical and cosmetic composition and its applications in metabolic corrections of aging and ischemic cells, Sephar, France (Apr 11, 2008)
3. G Korinth et al, Enhancement of percutaneous penetration of aniline and o-toluidine in vitro using skin barrier creams, Toxicology in Vitro 22(3) 812–818 (2008) (in English)
4. K Sugimoto et al, Development of alpha-arbutin: Production at industrial scale and application for a skin-lightening cosmetic ingredient, Trends in Glycoscience and Glycotechnology 19(110) 235–246 (2007) (in English and Japanese)
5. JA Bouwstra et al, Skin lipid organization, composition and barrier function, IFSCC 10(4) 297–307 (2007) (in English)
6. Y Kobayashi et al, Increased carbonyl protein levels in the stratum corneum of the face during winter, Intl Jrnl of Cosm Sci 30(1) 35–40 (2008) (in English)
7. I Iwai et al, Change in optical properties of stratum corneum induced by protein carbonylation in vitro, Intl Jrnl of Cosm Sci 30(1) 41–46 (2008) (in English)
8. Ikeda T et al, Property of the functional raw materials for hair care, Frag Jrnl 35(6) 55–60 (2007) (in Japanese)
9. T Doering et al, Super mild oxidation coloring: Preventing hair damage at the molecular level, IFSCC 10(4) 323–329 (2007) (in English)
10. EP 1,911,435, Two-phase composition for improving curl retention, KPSS-Kao Professional Salon Services GmbH, Germany (Apr 16, 2008)
11. F Guala et al, Oleoyl sarcosine: New perspectives and applications, Rivista Italiana delle Sostanze Grasse 84(4) 237–245 (2007) (in English)
12. S Daikai, Development and application of a novel amino acid derivative and a novel peptide derivative for hair care, Frag Jrnl 35(6) 49–54 (2007) (in Japanese)
13. JP 2008 88,148, Damaged hair-repairing agents and hair cosmetics containing methacrylate copolymers, Daito Chemical Industry Co, Ltd, Japan (Apr 17, 2008)
14. FR 2,907,005, Use of orcein for the coloring of human hair, L’Oréal, France (Apr 18, 2008)
15. FR 2,907,004, Method for dyeing of hair by means of a styrylic or iminic dye in combination with a zinc salt, L’Oréal, France (Apr 18, 2008)
16. WO 2008 46,795, Use of C10-14 alkanediols in the preparation of a composition for the prophylaxis and/or treatment of malassezia-induced dandruff formation, Symrise GmbH & Co, K-G, Germany (Apr 24, 2008)
17. L Durand et al, Influence of different parameters on droplet size and size distribution of sprayable sunscreen emulsions with high concentration of UV-filters, Intl Jrnl of Cosm Sci, 29(6) 461–471 (2007) (in English)
18. L von Oppen-Bezalel, UVA, a main concern in sun damage: Protection from the inside and outside with phytoene, phytofluene, the colorless carotenoids and more, SOFW Jrnl 133(11) 29–30, 32, 34 (2007) (in English)

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