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A Response........ 3

Dear Oilgae friends,
first of all an excuse to all the ones that have written to me and which I have not answered yet. Please forgive me - it is not that I am lazy - but a project in Africa where we might insatll a biogas unit with attached algae bio- reactor to capture the CO² - all that for a cattlefarming/meat production industry to get ridd if former disturbing an polluting abattoir waste and liquid manure by bio fermentation, methan gas production for generating electricity and nutrient rich feed supply with the same (I might give a detailed discription of these synergies later9, has kept me busy for a long time.

Never the less do I think it is time to give some examples again how to use algae other than burning it up to extend the live of fossile technology...........

Algae as a Source of Pharmaceuticals & Nutraceuticals

This article here on OILGAE calls for further information and clarification about this item.

While microalgae can be cultivated in PBR`s or ponds, the major part of macro algae usefull for pharmaceutical and cosmetic  applications live in the oceans . The biological effectiveness of these medical/cosmetic compounds on algae basis and their quality strongly depends on their origin, time of harvest, method of harvest and  the treatment and conversion. Often used macro algae harvesting methods are “trawlers” ripping the algae species out of their seabed, but also the collection of algae material from the beaches and shores after heavy storm is being practised. Due to the growing demand this methods are neither economical nor very sustainable – in fact it`s just another violation of natures resources.

This asks for a careful cultivation method that takes nature and the preservation of biodiversity into consideration. Here I would like to describe a macro algae cultivation method for the species Saccharina latissima syn. Laminaria saccharina.

For the culturing and easy harvest of Laminaria it is the best method to get the spores of this algae specie onto a culturing rope. This happens in specially designed pools where pieces of 1000 meters rope are being  prepared for so to be set out in open seawater. Artificial nutrients are not welcome and not necessary as these pools are being floated with fresh seawater. During this process the temperature has to be cooled down to under 18 degrees (for this type- Laminaria).

Marine algae reproduce similar to ferns or fungi by spores. This approach will help to settle the spores onto the culturing ropes to develop the algae body of the leaf-like “Phylloid”, the stem-like “Cauloid” and the root-like “Rhiozid”.

At the junction between Cauloid and Phylloid there is a regenerative zone, the “Meristem” which enables the algae to grow again after the algae has being cut of or died off. When harvesting it is therefore important to cut off the algae above this regenerative zone. If all the growing ropes are taking in – again new lines have to be prepared according to above giving procedure.

Extractable compounds:

These macro algae are rich on vitamins, minerals and trace elements which the algae accumulates in form of a great number of different polysaccharides from the ocean waters and thus making them available for a great number of health/healthcare products. Beside calcium, magnesium, iron and potassium they contain trace elements like iodine, cobber, zinc, selenium as well as manganese, strontium, molybdenum and germanium. This wide range of vitamins includes beside the vitamins A, C and E, niacin and folic acid the whole vitamin B-complex including the vitamin B-12 which otherwise is only present in animal products. All these components are important for our immune defence but also for the skin, the hair and nails and the connective tissue.

High-grade unsaturated fatty acids:

Algae are the only source  for eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) which are elsewhere only present in fish oil because they are accumulated through their food chain. These seldom  omega-3 fatty acids are among others extremely important fort the membrane stability especially of the skin.

Mycosporine-like amino acids (MAA)

Some of  the algae, but as well other organisms are building mycosporine like amino acids (MAA), UV-light absorbing substances (see former article >>> Light Management!) serving as “natural sunscreen”. They are absorbing shortwave sun rays und convert them into harmless heat.

Polysaccharides:

Of special significance for the cosmetic industry are the outstanding polysaccharides which are present in different types of algae, performable in  red- and brown macro algae. Here we can name the alginic acids and their salts, - alginate, carrageenan as well as fucoidan, glucans, fucose and other, partly yet unknown algae sugars.

a. alginic acids and alginate:

Brown algae contain as a characteristic compound of their cell walls mainly phycocolloid fucoidan and alginate, salts of alginic acids. The alginate contents depends on specie and which season of the year and can be between 15 – 40% of the dry-weight. For the production of alginate compounds only the few sort from the genus Laminariales (specie Saccharina) and Fucales (specie Fucus) are in use today. Worldwide yearly production of alginate is approx. 40.000 tonnes. The greatest producers are the USA, France, Norway, Great Britain, Canada, Japan and China.

Alginic acid ( INCI-term: ALGIN) is a mixture from polyuronic acids with changing amounts of 1,4-ß-D-mannuronic acid and 1,4-α-L-guluronic acid. In relation to the dry-weight alginic acid  contains a minimum of 19%, the most 25% carboxyl groups, whereby as small part can be neutralized. The alginate molecules are placed as tight packed strands in the cell-walls, whereby the carboxylate groups from uronic acids are tied together by bivalent cations as there are Ca²+ and Mg²+ as well as other trace elements. The molecular mass of native alginic acid lies between 150.000 and 250.000 Da. During the isolation process a degradation takes place that can lead to a molecule mass between 30.000 and 60.000 Da. This very different relation of the molecular strands has great influence on the viscosity quality of the final product.

Not only in the cosmetic industry, also in other areas, as there is the food-industry, pharmaceutical industry and the medicine, alginic acids and their salts are being used for theit characteristic   sol – and gel properties, their emulsion and suspension stabilising effect as well as their film forming ability and for the cation exchange (quantity of positively charged ions (cations).

Some products are: Sodium alginate- calcium salt mixtures for dental impression materials and also calcium alginate is being used as absorbent material for interactive wound dressing, sodium alginate in  spray plasters and wound dressings. The wound material has a styptic and curing effect as a “hämostypticum” as it immediately forms, when in contact with blood and its Ca²+ content, a membrane of unsolvable calcium alginate serving as protective colloid, sealing the wound.

b. Carrageen and carragenane:

Carrageene (INCI: CARRAGENAN)  is an umbrella term for a number of different polysaccharides produced by special macro red algae species. Different organic compounds are distinguished  by their amount of  galactose and 3-anhydrogalactose as well as their number of sulphate groups. Of interest for industrial use are premolar κ-, І- und λ-Carrageen, which all are different in their physicochemical characteristics. Also offered under the product name Carrageenane are commercial products with very different solution – and gel forming characteristics. These are mostly alkali treated carrageen or extracts or extracts fractions. Carragen finds its use in the food industry as gelling- and thickening agent. The cosmetic industry uses it for the production of toothpaste. Presently production culture of different red-algae species is going on in the Philippines, whereby it has been achieved to produce homogenous and commercial interesting types of carrageen.

c. ß-1,3-glucane

This polysaccharide from algae shows in a great number of trials immune activating qualities (macrophages) and are therefore being used for the treatment of cancer. In particular  phycarin stimulates the  humoral and cellulare  immune response through an inter-action with CD11b / CD18 receptors.  The anti-inflammatory effect of phycarin  is attributable to the p-selectine inhibition, whereby the molecular size and the degree of sulfation  are of great importance. Luminaran, the storage substance of the brown-algae belongs as well to the important β-1,3- glucanes, showing heparin- like characteristics and stimulates the immune system as well.

d) fucoidan

 

The phycocolloide fucoidane is typical for the brown algae and only produced by them. Neither in other algae species, nor in other plants has this phycocolloide been detected. According to the IUPAC definition are sulphated fucanes polysaccharides, mainly consisting of sulphated L-fucose (6-Deoxy-L-Galactose) containing less than 10% of other monosaccharides. Structural research has shown that fucoidane is not a homogenous  class of substance, but with great difference in terms of  molecular masses, grade of sulfation as well as its pattern. There are as well a number of variations in the glycosidic fixations and the sugar composition. Typical structural feature are α-1,4-linked L-Fucose-4-O-sulfat-units, which are ramified in position 2, acetylated or substituted with a second sulphate group. Beside all this there are also α-1,4- and α-1,2-linkrd fucose compositions with or without a sulphate group or a ramification.

 

Fucoidane became more and more of interest for science in these last years for their great variety of pharmacological properties. Anti-coagulation, antithrombotic activity, carcinostatic and immune modulating properties, enormous antioxidative effect, reduction of blood fat values, the anti-complement activity and anti-inflammatory effects. Of further interest in all this combination is a distinctive antiviral activity such as herpes viruses as well. The use of fucoidane for cosmetics is based on research about the effects on certain main requirements.

A stimulating effect of low-molecular fucoinade on the collagen synthesis was verified and the anti-aging-effect are explained to be the result of a reduction of skin thickness due to the use of extracts containing aqueous fucoidane containing solutions which also enhance the elasticity of the skin.

 

e. Oligo- and polysaccharide rich with fucose (FROP)

These fucose-rich polymeric carbohydrate structures are playing their role in cell-cell contacts and cell-matrix junctions. They stimulate the cell proliferation. Suppressing  the  metallo- protein matrix (MMP) and stimulating the collagen and elastin synthesis in fibroblasts increases the  elasticity of the skin and connective tissue and influence the aging effect.


Publications about the extractable compounds of Laminaria:

Pubmed  All publication can be found on Pubmed.

Aguilera J., Dummermuth A., Karsten u., Schriek R., Wiencke Ch. (2002) Enzymatic defences against photooxidative stress induced by ultraviolet radiation in Arctic marine macroalgae, Polar biology 2002, vol. 25, no 6, pp. 432-441


Aquaron R., Delange F., Marchal P., Lognoné V., Ninane L. (2002) Bioavailability of seaweed iodine in human beings., Cell Mol Biol (Noisy-le-grand). 2002 Jul;48(5):563-9

As an important fraction of consumers in the world prefers natural products over artificial ones, we investigated the industrial feasibility of naturally iodized salt using seaweed as source of iodine.  

Bayerisches Landesamt für Gesundheit und Lebensmittelsicherheit, Untersuchungsergebnisse 2008: Jod- und Schwermetallgehalte in algenhaltigen Kosmetika  

Bilan M.I., Grachev A.A., Shashkov A.S., Kelly M., Sanderson C.J., Nifantiev N.E., Usov A.I. (2010) Further studies on the composition and structure of a fucoidan preparation from the brown alga Saccharina latissima., Carbohydr Res. Vol. 345(14):2038-47.

In accordance with the previous data, the main polysaccharide component was shown to be a fucan sulfate [...]. In addition, three other types of sulfated polysaccharide molecules were detected in the total fucoidan preparation [...]. 

Brunschweiger E.-M., Pharmakologische Wirkung von Meerwasser, in: Schleswig-Holsteinisches Ärzteblatt 6/2005, S. 68-72

Bundesamt für Risikobewertung (BfR), Gesundheitliche Risiken durch zu hohen Jodgehalt in getrockneten Algen, aktualisierte Stellungnahme Nr. 026/2007 des BfR vom 22. Juni 2004

Bund/Länder-Messprogramm Meeresumwelt (BLMP), 2005: Zustandsbericht 1999–2002 für Nordsee und Ostsee 

Croci D.O., Cumashi A., Ushakova N.A., Preobrazhenskaya M.E., Piccoli A., Totani L., Ustyuzhanina N.E., Bilan M.I., Usov A.I., Grachev A.A., Morozevich G.E., Berman A.E., Sanderson C.J., Kelly M., Di Gregorio P., Rossi C., Tinari N., Iacobelli S., Rabinovich G.A., Nifantiev N.E. (2011) Fucans, but Not Fucomannoglucuronans, Determine the Biological Activities of Sulfated Polysaccharides from Laminaria saccharina Brown Seaweed., PLoS One. 6(2):e17283.

Thus, sulfated fucans are mainly responsible for the anti-inflammatory, anticoagulant, antiangiogenic, and antitumor activities of sulfated polysaccharides from L. saccharina brown seaweed. 

Cumashi A, Ushakova NA, Preobrazhenskaya ME, D'Incecco A, Piccoli A, Totani L, Tinari N, Morozevich GE, Berman AE, Bilan MI, Usov AI, Ustyuzhanina NE, Grachev AA, Sanderson CJ, Kelly M, Rabinovich GA, Iacobelli S, Nifantiev NE (2007) A comparative study of the anti-inammatory, anticoagulant, antiangiogenic, and antiadhesive activities of nine different fucoidans from brown seaweeds., Glycobiology vol. 17 no. 5 pp. 541–552

All fucoidans inhibited leucocyte recruitment in an inflammation model in rats, and neither the content of fucose and sulfate nor other structural features of their polysaccharide backbones significantly affected the efficacy of fucoidans in this model.

Davis T.A., Voleskya B., Mucci A. (2003) A review of the biochemistry of heavy metal biosorption by brown algae., Water Research 37 (2003) 4311–4330

More specifically, it is the properties of cell wall constituents, such as alginate and fucoidan, which are chiefly responsible for heavy metal chelation.

Dawczynski Ch., Schubert R., Jahreis G. (2006) Amino acids, fatty acids, and diatary fible in edible seaweed products, Food Chemistry 103 (2007) 891-899

Interestingly, the FA distribution of seaweed products showed high levels of n-3 FA and demonstrated a nutritionally ideal n-6/n-3 FA ratio. The predominante FA in various seaweed products was eicosapentaenoic acid (C20:5,n-3) which was at concentrations as high as 50% of total FA content.

Dawczynski C., Schäfer U., Leiterer M., Jahreis G. (2007) Nutritional and toxicological importance of macro, trace, and ultra-trace elements in algae food products., J Agric Food Chem. 2007 Dec 12;55(25):10470-5

 

Douady D., Rousseau B., Caron L. (1994) Fucoxanthin-chlorophyll a/c light-harvesting complexes of Laminaria saccharina: partial amino acid sequences and arrangement in thylakoid membranes., Biochemistry. 1994 Mar 22;33(11):3165-70

Drozd N.N., Tolstenkov A.S., Makarov V.A., Kuznetsova T.A., Besednova N.N., Shevchenko N.M., Zvyagintseva T.N. (2006) Pharmacodynamic parameters of anticoagulants based on sulfated polysaccharides from marine algae., Bull Exp Biol Med. 2006 Nov;142(5):591-3

Fodil-Bourahla I, Bizbiz L, Schoevaert D, Robert AM, Robert L. (2003) Effect of L-fucose and fucose-rich oligo- and polysaccharides (FROP-s) on skin aging: penetration, skin tissue production and fibrillogenesis., Biomed Pharmacother. 2003 Jul-Aug;57(5-6):209-15

These results, together with the previous favorable activities on the downregulation of matrix-degrading enzymes, free radical scavenging and increased cell proliferation confirm the favorable action of fucose and fucose-rich polysaccharides (FROP-s) on the skin by slowing down its aging.

Fujimura T., Tsukahara K., Moriwaki S., Kitahara T., Sano T., Takema Y. (2002) Treatment of human skin with an extract of Fucus vesiculosus chanoes its thickness and mechanical properties, J. Cosmet. Sci., 53, 1-9

In this study, they investigated the effects of topical application of an aqueous extract of this alga on the thickness and the mechanical properties of human skin. [...] These results suggest that the Fucm vesiculosus extract possesses anti-aging activities and should be useful for a variety of cosmetics.

Guiry M.D. and Blunden G. (1991) Seaweed Ressources in Europe: Uses and Potential

Han J., Kang S., Choue R., Kim H., Leem K., Chung S., Kim C., Chung J. (2002) Free radical scavenging effect of Diospyros kaki, Laminaria japonica and Undaria pinnatifida., Fitoterapia. 2002 Dec;73(7-8):710-2

Isnard N, Fodil-Bourahla I, Robert AM, Robert L. (2004) Pharmacology of skin aging. Stimulation of glycosaminoglycan biosynthesis by L-fucose and fucose-rich polysaccharides, effect of in vitro aging of fibroblasts., Biomed Pharmacother. 2004 Apr;58(3):202-4

These stimulations of GAG-biosynthesis might play a role in the increase of total skin thickness of hairless rats treated with L-fucose, as well as in several other favorable results recorded for FROP-3 such as the increased hydration (resistance to pressure) and elasticity of human skin

Jin D.Q., Li G., Kim J.S., Yong C.S., Kim J.A., Huh K. (2004) Preventive effects of Laminaria japonica aqueous extract on the oxidative stress and xanthine oxidase activity in streptozotocin-induced diabetic rat liver., Biol Pharm Bull. 2004 Jul;27(7):1037-40

The results suggest that Laminaria japonica would be of great value in preventing hyper-glycemia in diabetes mellitus as a dietary supplement possibly, through its antioxidant activity.

Kim K.H., Kim Y.W., Kim H.B., Lee B.J., Lee D.S. (2006) Anti-apoptotic activity of laminarin polysaccharides and their enzymatically hydrolyzed oligosaccharides from Laminaria japonica., Biotechnol Lett. 2006 Mar;28(6):439-46

These results suggest that laminarin oligosaccharides and polysaccharides can be utilized to develop new immunopotentiating substances and functional alternative medicines.

Küpper F.C., Carpenter L.J., McFiggans G.B., Palmer C.J., Waite T.J., Boneberg E.M., Woitsch S., Weiller M., Abela R., Grolimund D., Potin P., Butler A., Luther G.W. 3rd, Kroneck P.M., Meyer-Klaucke W., Feiters M.C. (2008) Iodide accumulation provides kelp with an inorganic antioxidant impacting atmospheric chemistry., Proc Natl Acad Sci U S A. 2008 May 13;105(19):6954-8

Using x-ray absorption spectroscopy, we show that the accumulated form is iodide, which readily scavenges a variety of reactive oxygen species (ROS). We propose here that its biological role is that of an inorganic antioxidant, the first to be described in a living system. ... In a complementary set of experiments using a heterologous system, iodide was found to effectively scavenge ROS in human blood cells.

Li N, Zhang Q, Song J (2005) Toxicological evaluation of fucoidan extracted from Laminaria japonica in Wistar rats., Food Chem Toxicol. 2005 Mar; 43(3):421-6

The results showed that no significant toxicological changes were observed when 300 mg/kg body weight per day fucoidan was administered to rats.

Neyrinck A.M., Mouson A., Delzenne N.M. (2007) Dietary supplementation with laminarin, a fermentable marine beta (1-3) glucan, protects against hepatotoxicity induced by LPS in rat by modulating immune response in the hepatic tissue., Int Immunopharmacol. 2007 Dec 5;7(12):1497-506 , Comment in: Int Immunopharmacol. 2008 Mar;8(3):514-5; discussion 516-7

Nishide E., Anzai H., Uchida N. and Nisizawa K. (1990) Sugar constituents of fucose-containing polysaccharides from various Japanese brown algae., Hydrobiologia Vol. 204-205, No. 1

Passaquet C., Thomas J.C., Caron L., Hauswirth N., Puel F., Berkaloff C. (1991) Light-harvesting complexes of brown algae. Biochemical characterization and immunological relationships., FEBS Lett. 1991 Mar 11;280(1):21-6

 

Péterszegi G, Robert AM, Robert L. (2003) Protection by L-fucose and fucose-rich polysaccharides against ROS-produced cell death in presence of ascorbate., Biomed Pharmacother. 2003 May-Jun;57(3-4):130-3

It appeared that relatively low concentrations of L-fucose and FROP-3 (Biomed. Pharmacother. in press) could efficiently protect fibroblasts from the ascorbate-induced cell-death. These novel pharmacological properties of L-fucose and FROP-3 might well be related to their accelerating effect of wound healing.

Robert L, Fodil-Bourahla I, Bizbiz L, Robert AM. (2004) Effect of L-fucose and fucose-rich polysaccharides on elastin biosynthesis, in vivo and in vitro., Biomed Pharmacother. 2004 Mar;58(2):123-8

These results show that L-fucose and FROP-3 stimulate tropoelastin biosynthesis in vitro, and elastic fibre formation in vivo.

Sánchez-Machado D.I., López-Hernández J., Paseiro-Losada P., López-Cervantes J. (2004) An HPLC method for the quantification of sterols in edible seaweeds., Biomed Chromatogr. 2004 Apr;18(3):183-90

The predominant sterol was fucosterol in brown seaweeds (83-97% of total sterol content)

Senni K., Gueniche F., Foucault-Bertaud A., Igondjo-Tchen S., Fioretti F., Colliec-Jouault S., Durand P., Guezennec J., Godeau G., Letourneur D. (2006) Fucoidan a sulfated polysaccharide from brown algae is a potent modulator of connective tissue proteolysis., Arch Biochem Biophys. 2006 Jan 1;445(1):56-64.

Using tissue sections of human skin in ex vivo experiments, we evidenced that this polysaccharide was able to minimize human leukocyte elastase activity resulting in the protection of human skin elastic fiber network against the enzymatic proteolysis due to this serine proteinase.

Stengel D.B., Macken A., Morrison L., Morley N. (2004) Zinc concentrations in marine macroalgae and a lichen from western Ireland in relation to phylogenetic grouping, habitat and morphology., Mar Pollut Bull. 2004 May;48(9-10):902-9

Sugawara T., Matsubara K., Akagi R., Mori M., Hirata T. (2006) Antiangiogenic activity of brown algae fucoxanthin and its deacetylated product, fucoxanthinol., J Agric Food Chem. 2006 Dec 27;54(26):9805-10

Usov A.I. ; Smirnova g.p. ; Bilan M.I. ; Shashkov A.S. (1998) Polysaccharides of Algae. 53. Brown Alga Laminaria saccharina (L.) Lam. as a Source of Fucoidan , Russ J Bioorgan Chem (1998) 24:437–445.

Fucoidan was found to contain L-fucose and sulfate as major components and galactose, xylose, and glucuronic acid as minor components.

Voronova Y.G., Rekhina N.I., Nikolaeva T.A., Tiunova N.A., Zailina I.V., Kobzeva N.YA., Valiente O. (2006) Extraction of carbohydrates from Laminaria and their utilization, Journal of Applied Phycology (2006) Vol. 3, No. 3

Wang J., Zhang Q., Zhang Z., Li Z. (2008) Antioxidant activity of sulfated polysaccharide fractions extracted from Laminaria japonica., Int J Biol Macromol. 2008 Mar 1;42(2):127-32

The correlation between the sulfate content and scavenging superoxide radical ability was positive. Available data obtained with in vitro models suggested that the ratio of sulfate content/fucose was an effective indicator to antioxidant activity of the samples.

Xue Chang-Hu, Yu Fang, Hong Lin, Lei Chen, Li Zhao-Jie, Deng Deng, Lu Chong-Xiao (2001) Chemical characters and antioxidative properties of sulfated polysaccharides from Laminaria japonica, Journal of Applied Phycology (2001) Vol. 13, No. 1

Yan X., Zheng L., Chen H., Lin W., Zhang W. (2004) Enriched accumulation and biotransformation of selenium in the edible seaweed Laminaria japonica., J Agric Food Chem. 2004 Oct 20;52(21):6460-4

This implied that kelp L. japonica could effectively transform inorganic selenium into organic selenium through metabolism.

Yuan Y.V., Walsh N.A. (2006) Antioxidant and antiproliferative activities of extracts from a variety of edible seaweeds, Food and Chemical Toxicology 44 (2006) 1144-1150

Zvyagintseva T.N., Shevchenko N.M., Nazarova I.V., Scobun A.S., Luk'yanov P.A., Elyakova L.A. (2000) Inhibition of complement activation by water-soluble polysaccharides of some far-eastern brown seaweeds., Comp Biochem Physiol C Toxicol Pharmacol. 2000 Jul;126(3):209-15

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