Sun Guard – Protection Against UVA Radiation

Photoaging: Exposure to ultraviolet light, UVA or UVB, from sunlight accounts for 90% of the symptoms of premature skin aging. Most of the photoaging effects occur by age 20. The amount of damage to the skin caused by the sun is determined by the total lifetime amount of radiation exposure and the person’s pigment protection.

Changes in the epidermis caused by the sun include thinning of the epidermis and the growth of skin lesions such as actinic keratoses, basal cell carcinomas, and squamous cell carcinomas.

Some other changes that occur due to photoaging include:
• Inelasticity of the skin
• Dryness and roughness of skin
• Skin’s color changes
• Freckles appear more often and are darker
• Sallowness (yellowish discoloration) appears
• Actinic/solar purpura (easy bruising) sets in
• Inability of the skin to protect itself from the development of skin cancer

Cosmetic ingredients that we use every day should be absolutely safe.

Mycosporine like amino acids, UVA sunscreens produced by certain algae, corals and zooplankton, are a natural and safe alternative to synthetic UVA sunscreens. These organisms that live in shallow water or at the beach where they are exposed to extreme UV radiation, produce the most powerful UV-absorbing substances in nature. A rich source of mycosporine like amino acids is the red alga Porphyra umbilicalis. This is the ingredient we add to some of our products as it is micro-encapsulated by Mibelle AG Biochemistry, a swiss cosmetic company, and marketed as a cosmetic ingredient with the brand Helioguard 365.
elioguard 365 contains isolated mycosporine like amino acids from the red alga Porphyra umbilicalis (INCI: Porphyra Umbilicalis) that are encapsulated into liposomes to increase their uptake by the skin. The isolated mycosporine like amino acids absorb maximally at 335 nm with a molar absorption coefficient of 45’000.

Test proves that Helioguard 365 protects against UVA
 
In a clinical study with 20 women a product with 5% Helioguard 365 was tested against a product with 1% Butyl Methoxydibenzoylmethane and 4% Ethylhexyl Methoxycinnamate. The test areas on the forearm were irradiated twice weekly with UVA. The irradiation dose of 10 J/cm2 corresponds to an average UVA exposure at a non-protected skin site. Helioguard 365 could reduce lipid peroxidation, the primary injure of UVA irradiation, as efficient as the product with synthetic filters. The product with Helioguard 365 prevented in this study the negative effects of UVA on skin firmness and smoothness even better than the product with synthetic filters.


UV-A sunscreen from red algae for protection against premature skin aging. Schmid Daniel, Schürch Cornelia and Zülli Fred, Mibelle AG Biochemistry.
The skin’s own UV defence system is not perfect. The solar radiation that reaches the earth’s surface ranges from 290 to 4000 nm. It can be separated into UV-B (290 – 320 nm), UV-A (320 – 400 nm), visible light (400 – 700 nm) and infrared radiation (700 – 4000 nm). UV radiation is damaging to a wide variety of biological systems. The highly energetic photons in these wavelengths cause damage to macromolecules such as DNA, proteins and membrane lipids. Nature has evolved a number of defense mechanisms to cope with UV radiation.
Synthesis of UV-screening compounds is almost ubiquitous. In humans, specified epidermal cells,
melanocytes, produce melanins in response to UV light. (Melanins are polymeric structures that are synthesized by the enzymatic oxidation of tyrosine.)

Protection by melanins is not always sufficient. Especially in summer time, higher energy UV-B can cause acute sunburn after exposure to direct sunlight. Whereas UV-B is retained in the upper epidermis UVA can reach the dermis where it is responsible for the premature skin aging effects of sun light. The fact that the skin on exposed areas such as the face and hands shows aging signs much earlier than protected skin sites clearly indicates UV as the principal etiologic factor in premature skin aging and indicates that melanin cannot completely protect against UV-A irradiation.

UV-A is the principal etiologic factor for premature skin aging.
Because UV-B is completely absorbed in the epidermis, it is UV-A that causes aging changes such as wrinkling, dryness and pigment abnormalities. UV-A alters the expression of certain genes by the generation of reactive oxygen species (ROS) and/or stimulation of proinflammatory cytokines such as IL-1β and TNF-α (Tebbe et al.). It has been shown that UV-A activates the transcription factors NF-κB and AP-1 (Djavaheri-Mergny & Dubertret). This results in the induction of a series of collagen and elastin degrading enzymes, the so called matrix metalloproteinases (MMPs).

A decrease in collagen content and fiber fragmentation ultimately leads to the typical signs of photoaging. ROS are formed after absorption of UV through skin chromophors, like urocanic acid or DNA. When UV light is absorbed by trans-urocanic acid (absorption maximum at 345 nm), singlet oxygen is generated. This highly reactive molecule can react with proteins or with lipids. The reaction products, such as lipid peroxides, are themselves ROS and have lost cellular functionality.

While UV-B is highly dependent on the season, daytime, cloudiness and latitude, UV-A is relatively constant during the year. In central Europe, erythemal UV-B is of minor importance in daily skin care products, but UV-A is present all year round at potentially harmful levels inside buildings as well as in the open air since UV-A easily penetrates window glass.

To estimate individual, daily UV exposure, test persons were equipped with small UV dosimeters (Rudolph & Träger). Exposure was measured on typical working days, taking into account indoor UV radiation. Their data show that inside buildings, UV-B levels are insignificant. A daily UV-B dose of 2.5 MEDs at an open window on a sunny summer day is reduced to 0.2 MED if the window is closed. In contrast, about 40% of the outdoor UV-A radiation dose could still be received indoors. Of real relevance for daily skin care are therefore not SPF factors but UVA protection.

This argues for the application of a daily UV-A protection ingredient. Although the percutaneous
absorption of synthetic UV-A sunscreens is low (Benech-Kieffer et al), there will be a substantial systemic accumulation when they are used daily, because day creams with UV-protection contain up to 1 to 5% pure synthetic UV-A sunscreens.

Natural UV-absorbing substances are suitable for daily skin care

The UV-screening substances of plants, phenolic acids and polyphenols, are already in use as the active molecules in a series of cosmetic products against photo-aging.

Red algae produces a technically and commercially applicable UV-A sunscreen
The strongest UV-A-absorbing compounds in nature are the mycosporine-like amino acids (MAAs). These are water-soluble substances found in a number of lower organisms such as cyanobacteria, red algae, dinoflagellates, corals and many marine invertebrates. The basic cyclohexanone or cyclohexenimine chromophore is responsible for UV absorption. Incorporation of various amino acids or iminoalcohol groups results in a diversity of about 20 MAAs (for a review see Cockell & Knowland).

Corals that live in clear shallow water, a UV-intense environment, are found to produce 13 different MAAs (Shick and Dunlap 2002). Mountain lakes are another UV intense environment, because exposure to UV increases with altitude and because the water is normally very clear so that UV can penetrate to depths of 20 m. Seven different MAAs were detected in the zooplankton of mountain lakes in the Central Alps (Sommaruga).

The red alga Porphyra umbilicalis is reported to produce the MAAs Porphyra-334 (Figure 1) and Shinorine (Gröniger et al.). Their absorption coefficients (εmolar) at 334 nm are 42’300 and 44’700 respectively (for the spectrum see Figure 2). Their filter capacity is therefore similar to that of synthetic UV-A sunscreens such as butyl methoxydibenzoylmethane (εmolar 40’000) and terephthalylidene dicamphor sulfonic acid (εmolar 45’000). P. umbilicalis lives in all oceans at the shore area on roughsurfaced rocks. It is a small alga, up to 20 cm, greenish when young and later purplish-red, with an irregularly shaped frond that is membranous but tough. P. umbilicalis, commonly known as Purple Laver in America and Europe or as Nori in Asia, is the most widely consumed seaweed in the world.

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