MARINE INGREDIENTS

Barbara Broakway IMCD, UK

Marine derived ingredients for personal care

The oceans and seas are a great place to find natural actives and functional materials for personal care products. They are the last great untapped resource. Despite covering more than 70% of the Earths surface, only a tiny proportion of their full potential is being used in personal care.1 We are familiar with using marine materials. We use everything from seawater to a huge range of extracts made from seaweed, microalgae, plankton, coral and many other marine organisms in personal care, but this is just the tip of the potential commercial iceberg. Formulations can be readily thickened or gelled with carrageenan, alginates (cold-soluble and cold-setting), agar or agarose, (all extracted from seaweed). Even the sand, mud and silt that settle on the ocean floor can have a place in cosmetics. The most exciting new materials come from the very deep sea and the water below 1,500 metres remains largely unexplored. This is the largest habitat on Earth (covering more than 60% of our planet). The clich that more people have travelled into space than have travelled to the deep ocean may have become a little overused but it does help get into perspective the remoteness of Earths flooded basement, the abyssal zone (see Fig. 1).2 firsthand experience of seawater helping their cuts to heal. The high sodium chloride content of seawater makes it difficult to use in formulas, so Soliance in France supply marine water which has suitably adjusted levels of salts, to help formulators get around the difficulties of using untreated salt water in formulas. This spring seawater has been clinically tested and shown to improve dry and damaged skin.5 Sea salt and salt from the Dead Sea are especially popular for anhydrous salt scrubs. Soaking in Dead Sea salts has been reported to help sufferers of rheumatoid arthritis, psoriatic arthritis, and osteoarthritis. The minerals are absorbed while soaking, stimulating blood circulation.6 Skin disorders such as acne and psoriasis benefit from regular soaking in reconstituted Dead Sea salt. The National Psoriasis Foundation recommends Dead Sea and Dead Sea salts as effective treatments for psoriasis. The high concentration of bromide and magnesium in the Dead Sea salt can relieve allergic reactions. One efficacy study showed bathing in the Dead Sea salt solution significantly improved skin barrier function compared with the tap watertreated control forearms. Another study saw a 40% reduction in the depth of wrinkles when skin was treated with reconstituted Dead Sea salts.7

The estaurine and euphotic zone

Abrasive sands of all grades and colours can be obtained for personal care use and are wonderful for treating hard skin on feet and elbows. Active Concepts can supply ABS Sea Silt Extract, which is water extracted marine silt (Maris limus).

Micromarine life

Seawater and sea salt

The most obvious marine ingredient is seawater. Thalassotherapy High tide (seawater therapy), has been used Low tide Sea level since Roman times.3 Unsurprisingly, Estuarine as terrestrial life originated in the seas, seawater contains an Continental shelf abundance of minerals essential for healthy skin. Naturally occurring Coastal minerals found in the sea include phosphorus, magnesium, zinc, iron, manganese, chromium, selenium, iodine and potassium and all have known skin benefits.4 There is a long safe history of traditional seawater therapies being used to treat common skin complaints. As more than half the worlds population live within 100 km of the coast, many people have The major life zones in an ocean. 70
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Euphotic Bathyal

Abyssal

A glass of seawater contains millions of bacterial cells, hundreds of thousands of phytoplankton and tens of thousands of zooplankton. New marine microlife is being discovered all the time. Unipex Innovations has worked with French Polynesian experts and collected Kopara from Moorea Island, also called the Magical Island, found among the volcanic islands and atolls located in the eastern South Pacific. Kopara is a unique ecosystem made up of communities of microorganisms that produce exopolysaccharide as protective shields. The polysaccharide enables them to survive being dried out and sun damaged at low tides.8 Scientists at Unipex Innovations have worked with isolates from Kopara and using various biotechnological techniques; and now produce locally three interesting exopolysaccharide actives (Exo H, Exo T and Exo P). Exo H (H for hydrating) has been shown to induce skin to produce hyaluronic acid, filaggrin and skin barrier lipids. It is therefore recommended for dry Sun skin and general skin improvement. Exo T (T for skin texture) triggers Open sea desquamation more effectively than retinoic acid. It is a potent inducer of differentiation markers. It protects the collagen network and so improves skin texture. Exo P chelates heavy metals on the skin surface9 and so helps protect skin against urban pollution and improves dull skin for a healthy look.10 Microalgae One class of marine microlife, the microalgae, are of huge global importance. Along with other phytoplankton they capture vast

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quantities of carbon dioxide from the atmosphere and help counteract the effects of carbon dioxide on global warming.11 They have also been heralded as the next big thing in green power as micro algae, such as Botryococcus braunii, will produce triterpene oil comparable in hydrocarbon content to petroleum. The cosmetic industry is fortunate to have suppliers who specialise in culturing strains of microalgae, which contain actives with proven cosmetic benefits. For example, Soliance in their Brittany laboratories culture Phaeodactylum tricornutum, which is typically found in Mediterranean coastal waters. Their Phaeodactylum tricornutum extract (Depollutine) has been shown to prevent ICAMs release from keratinocytes, so it is a useful active for stressed skin. Hence their trade name, Depollutine, which suggests its usefulness in products designed for people who live in cities and more polluted atmospheres. It is however very useful for all of us who live stressful lives. Skeletonema costatum is another coastal water microalgae that is being cultured in Brittany. It has a unique composition and is especially rich in essential amino acids. Skeletonema costatum extracts (Grevilline and Costalene) inhibit two key mediators to limit inflammation and reduce erythema.12 They also encourage strong intercellular junctions and are sources of beneficial omega-3 oils.16 Skeletonema costatum extract has been recommended for products designed to counteract the painful effects of sunburn and anti-ageing. Microalgae can also help moisturising the skin. Porphyridium cruentum extract (Porphyraline) is made from cultured red micro algae. It contains moisturising polysaccharides similar to human GAG, which create a protective coating. In nature, part of the polysaccharide dissolves in seawater and increases the local viscosity to protect the microalgae. Porphyridium cruentum is cultured in marine spring water, which is rich in various essential minerals.13 Phaeodactylum tricornutum, monocellular micro-algae, belonging to the Diatomophyceae is widely found in coastal waters of the Mediterranean, Brittany, Baltic and Caribbean. Phaeodactylum tricornutum extract (Megassine) has been shown to contain a specific poly unsaturated fatty acid as well as being a powerful antioxidant.14 It therefore has anti-ageing properties and its proteins are recognised as major targets for oxidative damage, like DNA and lipids. Chronological ageing and photo-ageing are mediated by depleted antioxidant enzyme expression leading to accumulation of harmful oxidised proteins and cellular dysfunction.5 Phaeodactylum tricornutum increases proteasome activity,

www.en.wikipedia.org Dozens

make soft beads, which look especially attractive in toiletries. These beads have more practical uses in other industries. For example they are used in biotechnology as tiny bioreactors. A bead can be easily made to contain living cells or enzymes by simply letting drops of alginate solution (containing cells or enzymes) fall into a solution of cross-linking calcium salts. These resulting beads are robust and have large surface areas, which makes them perfect supports for bioreactions. They can be easily swirled around a fluid filled fermenter tank and once a process is over, it is easy to drain away the media and recover the beads. Fermenting seaweeds Fermentation is an all natural process that can be used to create special new natural Ascophyllum nodosum. materials just as grape juice can be which are responsible for the removal of transformed into wine or vinegar. One of damaging protein oxidation products and the industrys most prestigious products, help maintain protein turnover. This is Crme De La Mer, claims to owe its efficacy especially important when skin is subjected to a highly potent fermented Miracle Broth to high UV irradiation.15 and its transformed ingredients - sea kelp, calcium, magnesium, potassium, iron, Seaweed lecithin, vitamins C, E and B12, plus citrus, eucalyptus, wheat germ, alfalfa and Extracts made from the many different sunflower oils. The process can take types of seaweed and simpler algae are 3-4 months to complete, but fermented also readily available as effective actives. seaweed still retains much of its polymer Active Concepts SRL supply ABS Alg moist structure so gives slip, body, and acts Eau, which is a popular moisturising seaweed extract. Wakamine from Soliance, as an excellent moisturiser. Fermentation improves bioavailability and by removing is a brown seaweed extract (Undaria less active, fermentable elements, brings pinnatifida). This golden-brown kelp from out actives, for example kelp has natural the Laminaria family grows in fairly anti-microbial properties. The fermenting protected waters such as bays and harbours. It is widely used in Japan where it microbes may synthesise essential fatty acids and vitamins so that the whole is traditionally added to miso soup (under process can be thought of as enriching a the Wakame name) and in China (as Qundai-cai).5 Small producers of seaweeds well-known marine active. Companies such as Active Concepts LLC offer a range of such as Roaring Water Bay Seaweed Cooperative Society and Cleggan Seaweeds fermented products including seaweed. in Ireland can be found throughout the Sponges and coral world. Their main products tend to be The greatest success stories for marine gelling agents such as carrageenan, actives in the pharmaceutical industry alginates, agar or agarose, all of which are come from the shallower regions of the extracted from seaweed. These polymers sea. The most profitable marine-derived have been used for thousands of years in drugs include the anti-viral acyclovir and its foods because they are very safe and excellent at controlling rheology and adding relative zidothymidine (AZT), which is used richness and body to all types of formulas. to delay development of AIDS, along with They are also useful polymers for improving the anti-cancer drug, Ara-C. These drugs owe their existence to materials originally stability, especially to help formulas survive freeze-thawing. Interestingly, they can give isolated from marine sponges. In the personal care industry, an extract made creams and lotions an attractive shine to their outer surfaces. These marine polymers from Caribbean sea whip (soft coral) Pseudopterogorgia elisabethae has been are excellent moisturisers. They can also the active ingredient in a few skin care be the backbone of face masks. FMC products for a number of years. The Biopolymers has an alginate powder blend commercially available cosmetic grade (Protanal FM 6130) that combines, at the extract is a partially purified extract of optimum ratios, diatomaceous earth with alginates and calcium salts to make a quick Pseudopterogorgia elisabethae that contains pseudopterosins (diterpenesetting face mask base. This base can be pentoseglycosides), which modify the used to carry a variety of anhydrous active inflammatory arachidonic acid cascade and ingredients. Alginates are also used to April 2012 P E R S O N A L C A R E 71

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are effective anti-inflammatory agents. Some marine organisms simply float on or spend much of their adult lives just below the surface of the water. If you have ever allowed yourself to slowly float on an air bed or spent a day snorkelling, you will know how hostile this region of the sea can be on a hot summers day. Left unprotected, human skin soon becomes inflamed and sun burnt. How do these organisms survive such hostile conditions? Hymeniacidon heliophila also known as the sun sponge is one such organism. It inhabits the inter-tidal waters off the coast of North Carolina. Hymeniacidon heliophila cells are rich in 5-hydoxytryptophan. This molecule has been shown to protect cells from UV damage. Interestingly, 5-hydoxytryptophan can be converted into serotonin in skin (a molecule associated with euphoria). It also, like caffeine, is a vasoconstrictor so, if it is applied to the skin near conspicuous veins, they will soon get smaller and appear less obvious. Extracts of Hymeniacidon heliophila have been shown by the scientists at Active Concepts LLC, to increase collagen synthesis by fibroblasts and to act as an antioxidant. The extract can therefore be useful for a number of cosmetics applications. The sun sponge extract would be useful therefore for anti-ageing products as well as for products designed to rapidly reduce the appearance of spider veins and dark areas under the eyes or perhaps better still, in sun care products.

Comb jellyfish.

acetylation, High Viscosity, 80%-90% degree of acetylation, Medium Viscosity, >80% degree of acetylation. It is used for its antimicrobial products especially in acne and antidandruff products. It will enhance the viscosity of various formulations. This natural polymer is a good film-former that is also moisturising. Its positive charge allows it to interact easily with biological surfaces such as skin and hair. It is effective in both cationic and non-ionic emulsions. Chitosan will help with hair curl retention. It leaves hair soft, silky and shiny hair and is good for controlling static and dry combing.9

with weakened immune systems (those ironically, that need it the most) so as, cold water fish oils are excellent sources of both EPA and DHA, which can be used directly, it makes good sense to use fish oils. EPA is converted in tissue to series 3 prostaglandins, which regulate, among other things, inflammatory responses (skin and joint) and immune function, arterial muscle tone, which involves blood pressure regulation. The series 1 and 2 prostaglandins have the exact opposite effect on the body as the series 3. They stimulate inflammation, constrict the arteries and inhibit immune response. That is why a properly balanced ratio of omega-3 (LNA, EPA and DHA) to omega-6 (linoleic acid: LA) is so critical for good health. There is mounting evidence that the lack of omega-3 oils and the excessive amount of omega-6 in the modern western diet lead to degenerative conditions.

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Sustainable management

Jellyfish
The 2010 BSB Innovations Award went to Oceanbasis for their jellyfish extract, with 2% marine collagen; it is an excellent moisturiser and forms a protective film on skin.

Crustacea
One major marine by-product is chitin. It is the main structural component of the shells of crustaceans. Chitin is difficult to dissolve so products usually use chitosan. Chitosan was first made in 1959, by Rouget who heated chitin with concentrated sodium hydroxide, which removed some of the acetyl groups from the molecular chain, leaving behind complete amino groups. By increasing the temperature or the strength of the sodium hydroxide solution, more acetyl groups could be removed. In this way, a range of chitosan molecules with different properties and applications have been made. Unlike chitin, chitosan dissolves easily organic acids and is a useful cationic polymer. It is sold under trade names such as Marine Biopolymer (MBP) at different grades for use in skin and hair care. Typical grades are as follows: Very High Viscosity, 75%-85% degree of 72
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Care is taken by suppliers to use marine materials from certified sources by recognised regional organisations. Using coral and soft coral has raised concerns in the industry as it is so easy to damage the marine ecology. Ten thousand pounds of Pseudopterogorgia elisabethae have been harvested from the coast of the Bahamas but researchers expect that this population will recover as Pseudopterogorgia elisabethae re-grows rapidly. With potent active materials that need Fish only be collected from the sea in small Fish are rarely caught to make cosmetic amounts, suppliers always look for ways ingredients. Fish elastin and collagen (and of culturing organisms rather than wild their hydrolysates) are made as by-products harvesting. Where materials must be of the huge fishing industry. These materials harvested in tonne quantities, it is agreed are extracted from the waste skin and that carrying out sustainable management bones. Care is taken by suppliers to only is paramount. FMC BioPolymers is one use fish waste from sources certified by company that harvests tonnes of brown recognised regional fisheries management seaweed from both warm and cold waters organisation or other organisations around the world and in return provides dedicated to the sustainable management economic development in coastal areas. of fisheries. Unipex Innovations MDI They know sound stewardship is essential complex is a very effective MMP inhibitor for maintaining an enduring supply. and perfect for firming, addressing dark They promote sustainable and regulated circles and general skin wellbeing and seaweed harvests. For example, FMC anti-ageing. This glycoaminoglycan is a BioPolymers Norwegian fleet of trawlers by-product of essential shark culling that harvests the alginate that grows in great takes place of the coast of Canada.9 abundance under the icy coastal waters. Fish oils include squalane (often from They adhere to a prescribed sustainable shark liver) and the much-needed poly management scheme working with the full unsaturated fatty acids. Remember, alphacooperation of the Norwegian government. linoleic acid (LNA) is plant-derived therefore The seaweed grows to maturity in five-year a botanical oil, which our bodies then cycles. The beds of brown seaweed off convert into eicosapentaenoic acid (EPA) Norways coast are divided into more than and docohexaenoic acid (DHA) in order 400 fields. The crop is carefully harvested for it to carry out the essential functions. by field, to allow re-growth and specially The body requires approximately ten LNA designed rakes pull mature plants off the molecules to produce one EPA molecule. ocean floor while leaving young plants to This conversion can be difficult or repopulate the area. Similar managed impossible for some older people or those harvests take place in Iceland, Morocco

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and off the coast of Canada. A different method is used in Australia, where seaweed is gathered as it washes ashore after a storm. In places like the Philippines, Indonesia, Tanzania and Madagascar, carageenophytes are cultivated and harvested in warm, shallow waters, giving employment to local communities who profit from this reliable cash crop. The approximately 230,000 known marine plant and animal species living in these upper regions of our seas, just 10% of our planet (mostly estuarine and euphotic zone), provide us each year with approximately 100 million tonnes of raw materials (most of which finds its way into food and then some into personal care). How much more is waiting for us?

The deep sea the abyssal zone

Both the pharmaceutical and personal care industries are driven by discovering new materials and so it is not surprising that already there are ingredients for personal care derived from microbes that live at these extreme depths. These few actives are just the first phase of what may turn out to be many phases of discoveries. Today, exploration is limited by the few submersibles capable of withstanding the pressures and travelling down to the abyssal plains and deep the ocean floor. However, the images they have captured have been used to make excellent documentaries such as the BBCs 2011 Deep Seabed in their Blue Planet series. Many shorter videos taken by these specialised craft show the unusual lifeforms that inhabit the deep ocean. They are readily available over the internet so all of us can now share the excitement of seeing these new-to-science extremophiles living their lives in, what for us would be impossible conditions, from the comfort of our more hospitable-to-us homes. Universities and scientific establishments such as the French Research Institute for Exploitation of the Sea (IFREMER) and Woods Hole Oceanographic Institution in Massachusetts have been studying the organisms recovered from these extreme depths. One special extracellular polysaccharide (Deepsane) has been isolated from cultured Alteromonas macleodii. This gammaproteobacterium strain normally lives in the sea at depths between 1000 m and 3500 m. The strain they have used is strictly aerobic, nonfermentative, non-luminescent, and nonpigmented. It is an encapsulated Gramnegative. Fortunately, this extremophile will grow at atmospheric pressure when its optimal growth conditions are between 30C-35C, pH 6.5-7.5 and the ionic strength between 20 g/L-40 g/L NaCl.

This is providential as many of the organisms who have adapted to these extreme conditions may not be able to survive at lower atmospheric pressures. Deepsane is now produced in amounts suitable for use in the personal care industry. It is known to be a large molecule made up of repeating units of eleven glycosidic residues. It contains glucose, galactose, rhamnose, fucose and mannose along with glucuronic and galacturonic acids. Deepsane is also characterised by an unusual sugar, a diacidic hexose identified as a 3-0-(1 carboxyethyl)-D-glucuronic acid. The strain of Alteromonas macleodii, cultured for Deepsane was harvested from the deepest oceans, situated at 13 North, near the Mexican coast. Scientists at IFREMER cultured the strain and first isolated Deepsane. They believe that Deepsane may be a key component of the filamentous microbial mat that forms around the deep-sea hydrothermal chimneys. These microbial mats are necessary to securely-anchored colonies so they can develop and thrive in the turbulent waters. They also help shield the microbes from the high concentrations of toxic substances, such as heavy metals, which are continually being spued out of the hydrothermal vents. Clinical studies have shown that Deepsane has cosmetic benefits. It is a very effective anti-inflammatory. It significantly reduces ICAM-1 expression while also protecting langerhans cells, which are essential players in the skins immune system. In addition, aqueous extracts containing Deepsane help repair damaged skin through IL-1 regulation. The studies indicate that Alteromonas ferment extracts, (Unipex Innovations Abyssine) which contains Deepsane, can help protect and encourage skin repair so are ideal for sensitive, reactive and damaged skin.9

Conclusion
There is no doubt that man does enjoy the sights and sounds of the ocean. Paradise is often portrayed as a desert island surrounded by blue seas so it is especially good to know that the oceans and seas are a great place to find natural actives and function materials for personal care products. An abundance of new interesting materials are keenly anticipated as the PC deep sea is more fully explored.

References
1 Ward A. Weighing earths water from space. (2003). http://earthobservatory.nasa.gov/ Features/WeighingWater 2 Yancy P The deep sea (2011). . http://marinebio.org/oceans/deep 3 Charlier RH, Chaineux MP The healing sea: . a sustainable coastal ocean resource: Thalassotherapy. Journal of Coastal Research 2009; 25 (4): 838-56. 4 Physical and thermodynamic data. (1997) Version 2.13, Ch. 5 pp 1-22. http://cdiac.esd.ornl.gov/ftp/cdiac74/chapter5.pdf 5 Soliance (2012) http://www.soliance.com 6 Harari M, Shani J. Demographic evaluation of successful antipsoriatic climatotherapy at the Dead Sea (Israel) DMZ Clinic. Int J Dermatol 1997; 36 (4): 304-5. 7 Proksch E, Nissen HP Bremgartner M, Urquhart C. , Bathing in a magnesium-rich Dead Sea salt solution: follow-on review. Int J Dermatol 2005; 46 (2): 177-79. 8 Jean Guzenneca J, Moppertb X, Ragunsa G, Richertb L, Costab B, Simon-Colina C. Process Biochemistry 2011; 46 (1): 16-22. 9 Unipex (2012) http://www.unipexinnovations.com/ en/index.php 10 Dweck A. Innovatary concepts reviewed. Personal Care 2009; 21-29. 11 Charleson RJ, Lovelock JE, Warren MO, Warren SG. Oceanic phytoplankton, atmospheric sulphur, cloud albedo and climate. Nature 1987; 326: 655. 12 Rocquet C, Reynaud R. A natural way to relieve the skin from erythema: Grevilline. Cosmetic Science Technology 2008. , , 13 Berg JP Debiton E, Dumay J, Durand P Barthomeuf C. In vitro anti-inflammatory and anti-proliferative activity of sulfolipids from the red alga Porphyridium cruentum. J Agric Food Chem 2002; 50 (21): 6227-32. 14 Rodriguez-Garcia I, Guil-Guerrero JL, Evaluation of the antioxidant activity of three microalgal species for use as dietary supplements and in the preservation of foods. Food Chemistry 2008; 108 (3): 1023-6. 15 Bulteau AL, Moreau M, Saunois A, Nizard C, Friguet B. Algae extract-mediated stimulation and protection of proteasome activity within human keratinocytes exposed to UVA and UVB irradiation. Antioxid Redox Signal 2006; 8 (1-2): 136-43. 16 Shaw PM, Jones GJ, Smith JD, Johns RB. Intraspecific variations in the fatty acids of the diatom Skeletonema costatum. Phytochemistry 1989; 28 (3): 811-5.

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