Helioguard 365 - Natural UV-A Skin Protection Against Photo-Aging
The principal etiologic factor in premature skin aging is UVA. In contrast to UVB, UVA is not much dependent on daytime and season and penetrates rather well through clouds and window glass. Our skin needs therefore help against the daily exposure to UVA and photoaging.
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 in Bio Beauty Balm as it is micro-encapsulated by Mibelle AG Biochemistry, a swiss cosmetic company, and marketed as a cosmetic ingredient with the brand Helioguard 365.
Helioguard 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.
The MAAs in P. umbilicalis from the Bretagne in France were analysed by HPLC. This algae material contained the MAAs Porphyra-334 and Shinorine, in a ratio of 2 : 1. The total MAA concentration was 1.4% of dry mass. This is considerably more than the reported typical concentration range of 0.16 to 0.84% (Cockell & Knowland).
Study on the activity of MAAs to protect against photo-aging
Normal UV-A exposure at non-protected skin areas is between 3 and 20 J/cm2. Rudolph and Träger measured an UV-A exposure of 8 J/cm2 at the outside of a forearm facing an open window during weather that was a mixture of cloudy and sunny periods. The irradiation dose that was applied in this study (two times 10 J/cm2 per week) therefore corresponds to an average UV-A exposure at a non-protected skin site.
Thus, the study mimics daily photo-aging of the skin.
UV-A radiation is a powerful generator of harmful radicals in our skin cells. The first targets are the lipids in the cell membranes that are oxidized to lipid peroxides. These lipid radicals stand at the beginning of a deleterious reaction sequence that finally ends in loss of skin resilience and formation of wrinkles (for a review see Pinnell & Durham). The formation of lipid peroxides in the test areas was measured after 28 days. Compared to the untreated test area, treatment with a cream containing 0.005% MAAs encapsulated in liposomes reduced lipid peroxidation by 37% (Figure 3). The capacity of the test product with MAAs to neutralize free radicals was as good as that of a product with synthetic filters (35% reduction), which contained 1% UV-A filter and 4% UV-B filter.
Free radicals that are produced upon exposure to UV radiation finally lead to photo-aging of the skin. These alterations in the skin are expressed in reduced firmness and smoothness. Application of the test product with MAAs encapsulated in liposomes could not only counteract these processes but even improve skin parameters during the study period. Both firmness and smoothness were significantly improved after four weeks, by 10% and 12% respectively (Figures 4 and 5). Using these parameters, the MAA test product performed clearly better than the product with the synthetic filters.
Improvement of skin firmness compared to the beginning of the study and the untreated area
The study clearly demonstrates that a cream with 0.005%
MAAs can neutralize UV-A effects as efficiently as a cream
with 1% synthetic UV-A filters and 4% UV-B filters. The
UV-B sunscreens are not relevant to this study because the
test areas were only exposed to UV-A irradiation. But as
outlined in the introduction, this corresponds to normal
working day situations in central Europe where only UV-A
effects are signficant.
Improvement of skin smoothness compared to the beginning of the study and the untreated area
Considering the UV-A-filtering capacity, the cream with 1% synthetic UV-A filter is 200 times more active than the MAA test product. The fact that this was not reflected in the study results (or even in the opposite way) indicates that the absorption capacity is not the only factor that is important for skin protection against photo-aging. Highly important is what happens to the screening compounds when they switch energy levels during absorption. The ideal sunscreen rapidly and effectively transforms absorbed UV into harmless thermal energy with no subsequent loss of protective power. It has been reported that butyl methoxydibenzoylmethane can partially decompose into inactive reaction products upon UV exposure (Chatelain & Gabard) and generates free radicals when illuminated (Damiani et al.).
Analysis of the photophysical and photochemical properties of MAAs showed their qualification as photo-protectors because they do not produce reactive intermediates upon irradiation (Conde et al).
Antioxidants present in the MAA extract might have also exerted a protective role in the photo-aging study. One of these antioxidants could be the MAA precursor molecule in the biosynthesis, 4-deoxygadusol. (Dunlap et al., 4th International Marine Biotechnology Conference, Sorrento, September 23, 1997).
Methods
HPLC-Analysis of MAAs.
Separation of MAAs was done on a Superspher 100 RP 18
column (4 _m, 254 x 4 mm) with a LiChrospher 100 RP 18
endcapt precolumn (5 _m). The mobile phase was 0.02%
acetic acid and the flow rate 1.0 ml/min. The detection
wavelength was 334 nm. Identification was done by comparison with MAA standards that were provided by Prof.
Dr. D.-P. Häder (Friedrich-Alexander University of
Erlangen, Germany).
Human study
Liposome encapsulated MAAs were prepared by extraction
of dried P. umbilicalis in water and subsequent
ultrafiltration and ion exchange chromatography of the
extract. For encapsulation this material was mixed with
lecithin by high pressure homogenization. The test
product was a cream with 5% MAA extract. The final
MAA concentration in the test product was 0.005%. The
cream with MAAs was compared to a cream with 4%
ethylhexyl methoxycinnamate and 1% butyl
methoxydibenzoylmethane. The cream without actives
served as control.
The study was conducted with 20 women in the age range 36 – 54. The test products were applied twice daily on defined sites on the inner side of the forearm. The test areas were irradiated twice weekly with UV-A (10 J/cm2). Skin elasticity (firmness) was measured with a Cutometer SEM 575. Skin roughness (smoothness) was determined with the digital micromirror device ‘PRIMOS’ (GFMesstechnik GmbH, Teltow, Germany). Skin hydration was measured with the Corneometer CM 825 PC. Lipid peroxidation was measured by HPLC.
Literature
• Benech-Kieffer F., Meuling W. J., Leclerc C., Roza L.,
Leclaire J. & Nohynek G. (2003) Percutaneous Absorption
of Mexoryl SX® in Human Volunteers: Comparison with in
vitro Data. Skin Pharmacol Appl Skin Physiol 16: 343-355.
• Chatelain E. & Gabard B. (2001) Photostabilization of
butyl methoxydibenzoylmethane (Avobenzone) and
ethylhexyl methoxycinnamate by bis-ethylhexyloxyphenol
methoxyphenyl triazine (Tinosorb S), a new UV broadband
filter. Photochem Photobiol 74: 401-406
• Cockell Ch. S. & Knowland J. (1999) Ultraviolet radiation screening compounds. Biol Rev 74: 311-345
• Conde F. R., Churio M. S. & Previtali C. M. (2000) The photoprotector mechanism of mycosporine-like amino acids. Excited-state properties and photostability of porphyra-334 in aqueous solution. J Photochem Photobiol B: Biol 56: 139-144
• Damiani E., Carloni P., Biondi C. & Greci L. (2000)
Increased oxidative modification of albumin when
illuminated in vitro in the presence of a common sunscreen
ingredient: protection by nitroxide radicals. Free Rad Biol
Med 28: 193-201
• Djavaheri-Mergny M. & Dubertret L. (2001)
UV-A-induced AP-1 activation requires the Raf/ERK
pathway in human NCTC 2544 keratinocytes. Exp
Dermatol 10: 204-210
• Gröniger A., Sinha R. P., Klisch M. & Häder D.-P. (2000) Photoprotective compounds in cyanobacteria, phytoplankton and macroalgae – a database. J Photochem Photobiol. B: Biology 58: 115-122
• Pinnell S. R. & Durham MD. (2003) Cutaneous
photodamage, oxidative stress, and topical antioxidant
protection. J Am Acad Dermatol 48: 1-19
• Rudolph T. & Träger Ch., 22nd IFSCC Congress Edinburgh 2002, oral presentations, volume 2.
• Sommaruga R. & Garcia-Pichel F. (1999) UV-absorbing mycosporine-like compounds in planktonic and benthic organisms from a high-mountain lake. Arch. Hydrobiol. 144: 255-269.
• Tebbe B., Wu S., Geilen Ch. C., Eberle J., Kodelja V. & Orfanos C. E. (1997) L-Ascorbic Acid Inhibits UVAInduced Lipid Peroxidation and Secretion of IL-1a and IL-6 in Cultured Human Keratinocytes In Vitro. J Invest Dermatol 108: 302-306.
Authors: Schmid Daniel, Schürch Cornelia and Zülli Fred Mibelle AG Biochemistry Bolimattstrasse 1 5033 Buchs, Switzerland Helioguard 365 - Natural Sunscreen for UV-A Skin Protection Against Photo-Aging
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Bio Beauty Balm deeply moisturizes and helps your skin adapt to stress every day thanks to rich biological adaptogens: Helix Aspersa Muller Glycoconjugates and Rhodolia Rose. Protects from solar damage with a liposomal preparation of mycosporine-like amino acids from the red sea algae Porphyra umbilicalis that have an absorption capacity comparable to synthetic UVA-Filters. Daytime balm for routine recovery of the skin from everyday stressors and the protection from the effects of solar radiation. Use it to help support the skin’s natural recovery from the visible effects of DNA damage and as an intense treatment for all types of skin conditions, including scars, keratosis pilaris, actinic keratosis, dryness and more... |
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BIO BEAUTY BALM ™ nourishes and protects your skin from the effects of solar radiation and other environmental stressors, while at the same time it enhances the dynamic interactions between skin and your nervous system, keeping you happy and your skin velvety soft, hydrated, and beautiful.
BIO BEAUTY BALM contains the exact same rich biological adaptogen found in BIOBALM ™ and a botanical adaptogen, rhodolia rose root extract which increases the consumption of oxygen at the cellular level and promotes the production of β-endorphins in the skin, thus producing inner wellness and relaxation that becomes manifest in the external appearance.
BIO BEAUTY BALM also contains a liposomal preparation of Mycosporine-like amino acids from the red sea algae Porphyra umbilicalis that have an absorption capacity comparable to synthetic UVA-Filters.
Remember that where ever you are, what ever you do, UVA-Rays penetrate 365 days a year into your skin. As they cannot be blocked by clouds or glass and do permanently cause irreversible damage to the skin, we all do need photo-protection – a NATURAL protection. And, since nowadays the ozone layer is rapidly depleting, our need for sun protection is greater than ever before.
Sunscreens, while effective barriers, only physically hinder UV damage. A second line of defense is imperative … That second line of defense is BIO BEAUTY BALM ™
