Structural characterization of laminaran and galactofucan extracted from the brown seaweed Saccharina longicruris.

Brown seaweed contains several polysaccharides like laminaran, fucoidan and alginate. Laminaran is a beta-glucan that has shown anti-apoptotic and anti-tumoral activities, while galactofucan (fucoidan) is a sulfated polysaccharide that has displayed anticoagulant, anti-tumor, anti-thrombosis, anti-inflammatory and antiviral properties. In this study, crude laminaran and galactofucan (fucoidan) were extracted from the brown seaweed Saccharina longicruris at four harvest periods (M05, A05, N05 and J06). The galactofucan M05 and N05 fractions were depolymerized (RDP) over 2 or 4h to give 4 RDP fractions (M05 RDP 2H, M05 RDP 4H, N05 RDP 2H and N05 RDP 4H) whose molecular weights, monosaccharide compositions and glycosidic linkages were determined by GC-MS. The laminaran fraction gave a molecular weight range from 2900 to 3300 Da and contained between 50.6% and 68.6% d-glucose and an average of 1.3% D-mannitol. The presence of a beta-(1,3) linkage between D-glucose in the main chain was observed, with branching at positions 6 and 2. The M05 fraction contained less branching than other laminaran fractions, which might have influenced its conformation in solution and thus its activity. The crude galactofucan fractions displayed a molecular weight range from 638 to 1529 kDa, whereas the RDP fractions had molecular weights <30 kDa. The structure of the galactofucan fractions remained complex after depolymerization, with these also being more sulfated (30-39%) than the crude fractions (13-20%). The crude and RDP fractions contained 3-linked fucopyranose 4-sulfate and 6-linked galactopyranose 3-sulfate moieties, although the galactofucans isolated from M05 and J06 contained less 6-linked galactopyranose 3-sulfate than the A05 and N05 fractions.

[1]  É. Deslandes,et al.  Estimation of the sulfate content of hydrothermal vent bacterial polysaccharides by Fourier transform infrared spectroscopy. , 1994, Analytical biochemistry.

[2]  Molecular dynamics study on the conformational stability of laminaran oligomers in various solvents. , 2000, Biomacromolecules.

[3]  A. Neyrinck,et al.  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. , 2008 .

[4]  Han-Bok Kim,et al.  Anti-apoptotic Activity of Laminarin Polysaccharides and their Enzymatically Hydrolyzed Oligosaccharides from Laminaria japonica , 2006, Biotechnology Letters.

[5]  N. Kervarec,et al.  Structural studies of the main exopolysaccharide produced by the deep-sea bacterium Alteromonas infernus. , 2004, Carbohydrate research.

[6]  E. Percival,et al.  Chemistry and enzymology of marine algal polysaccharides , 1967 .

[7]  V. Stonik,et al.  Fucoidan inhibits UVB-induced MMP-1 expression in human skin fibroblasts. , 2008, Biological & pharmaceutical bulletin.

[8]  C. Lane,et al.  A MULTI‐GENE MOLECULAR INVESTIGATION OF THE KELP (LAMINARIALES, PHAEOPHYCEAE) SUPPORTS SUBSTANTIAL TAXONOMIC RE‐ORGANIZATION 1 , 2006 .

[9]  A. Dell,et al.  Structural analysis of laminarans by MALDI and FAB mass spectrometry , 1998 .

[10]  O. Berteau,et al.  Sulfated fucans, fresh perspectives: structures, functions, and biological properties of sulfated fucans and an overview of enzymes active toward this class of polysaccharide. , 2003, Glycobiology.

[11]  P. Rupérez,et al.  Potential antioxidant capacity of sulfated polysaccharides from the edible marine brown seaweed Fucus vesiculosus. , 2002, Journal of agricultural and food chemistry.

[12]  M. Kizaki,et al.  Fucoidan induces apoptosis of human HS‐Sultan cells accompanied by activation of caspase‐3 and down‐regulation of ERK Pathways , 2005, American journal of hematology.

[13]  C. Sinquin,et al.  Relationship between sulfate groups and biological activities of fucans. , 2000, Thrombosis research.

[14]  P. Albersheim,et al.  Determination, by methylation analysis, of the glycosyl-linkage compositions of microgram quantities of complex carbohydrates , 1983 .

[15]  K. Fung,et al.  Polysaccharide biological response modifiers. , 2006, Immunology letters.

[16]  U Lindahl,et al.  Further characterization of the antithrombin-binding sequence in heparin. , 1982, Carbohydrate research.

[17]  S. Gordon,et al.  Differential High-Affinity Interaction of Dectin-1 with Natural or Synthetic Glucans Is Dependent upon Primary Structure and Is Influenced by Polymer Chain Length and Side-Chain Branching , 2008, Journal of Pharmacology and Experimental Therapeutics.

[18]  E. Damonte,et al.  Structural analysis and antiviral activity of a sulfated galactan from the red seaweed Schizymenia binderi (Gigartinales, Rhodophyta). , 2005, Carbohydrate research.

[19]  M. Fujihara,et al.  Isolation, purification, and characterization of fucose-containing sulfated polysaccharides from the brown seaweed Ecklonia kurome and their blood-anticoagulant activities. , 1989, Carbohydrate research.

[20]  K. Hayashi,et al.  Novel antiviral fucoidan from sporophyll of Undaria pinnatifida (Mekabu). , 2004, Chemical & pharmaceutical bulletin.

[21]  J. A. Guimarães,et al.  Conformation of sulfated galactan and sulfated fucan in aqueous solutions: implications to their anticoagulant activities. , 2007, Journal of molecular graphics & modelling.

[22]  J. Mollet,et al.  Yield, chemical composition and gel strength of agarocolloids of Gracilaria gracilis, Gracilariopsis longissima and the newly reported Gracilaria cf. vermiculophylla from Roscoff (Brittany, France) , 1998, Journal of Applied Phycology.

[23]  R. Williams,et al.  A revised structure for fucoidan may explain some of its biological activities. , 1993, The Journal of biological chemistry.

[24]  J. Kennedy,et al.  Carbohydrate analysis: a practical approach , 1986 .

[25]  S. Turgeon,et al.  Effect of season on the composition of bioactive polysaccharides from the brown seaweed Saccharina longicruris. , 2009, Phytochemistry.

[26]  N. Goasdoué,et al.  Degradation of algal (Ascophyllum nodosum) fucoidan by an enzymatic activity contained in digestive glands of the marine mollusc Pecten maximus , 1999 .

[27]  J. Joseleau,et al.  A fucoidan fraction from Ascophyllum nodosum. , 2001, Carbohydrate research.

[28]  C. Blondin,et al.  Anticoagulant low molecular weight fucans produced by radical process and ion exchange chromatography of high molecular weight fucans extracted from the brown seaweed Ascophyllum nodosum. , 1996, Carbohydrate research.

[29]  B. Matsuhiro,et al.  Preparation of a low-molecular weight fraction by free radical depolymerization of the sulfated galactan from Schizymenia binderi (Gigartinales, Rhodophyta) and its anticoagulant activity , 2006 .

[30]  Satoru Koyanagi,et al.  Oversulfation of fucoidan enhances its anti-angiogenic and antitumor activities. , 2003, Biochemical pharmacology.

[31]  M. Lahaye,et al.  Seaweed dietary fibres: structure, physico-chemical and biological properties relevant to intestinal physiology , 1997 .

[32]  B. Mulloy,et al.  A disaccharide repeat unit is the major structure in fucoidans from two species of brown algae. , 2001, Carbohydrate research.

[33]  S. S. Veiga,et al.  Structural and Hemostatic Activities of a Sulfated Galactofucan from the Brown Alga Spatoglossum schroederi , 2005, Journal of Biological Chemistry.

[34]  A. Bacic,et al.  Analysis of the structural heterogeneity of laminarin by electrospray-ionisation-mass spectrometry. , 1996, Carbohydrate research.

[35]  A. Dell,et al.  A study of fucoidan from the brown seaweed Chorda filum. , 1999, Carbohydrate research.

[36]  T E Nelson,et al.  Separation and characterization of the soluble and insoluble components of insoluble laminaran. , 1974, Carbohydrate research.

[37]  F. Chaubet,et al.  Further data on the structure of brown seaweed fucans: relationships with anticoagulant activity. , 1999, Carbohydrate research.

[38]  J. Kalbfleisch,et al.  The influence of glucan polymer structure and solution conformation on binding to (1-->3)-beta-D-glucan receptors in a human monocyte-like cell line. , 2000, Glycobiology.

[39]  P. S. Andrews,et al.  Effects of Sulphated Degraded Laminarin on Experimental Tumour Growth , 1963, British Journal of Cancer.

[40]  S. Hakomori A RAPID PERMETHYLATION OF GLYCOLIPID, AND POLYSACCHARIDE CATALYZED BY METHYLSULFINYL CARBANION IN DIMETHYL SULFOXIDE. , 1964, Journal of biochemistry.

[41]  J. Larochelle,et al.  AN ALTERNATE GROWTH PATTERN FOR LAMINARIA LONGICRURIS 1, 2 , 1981 .

[42]  P. Mourão,et al.  Is there a correlation between structure and anticoagulant action of sulfated galactans and sulfated fucans? , 2002, Glycobiology.

[43]  R. Furneaux,et al.  Structure and Antiviral Activity of the Galactofucan Sulfates Extracted from UndariaPinnatifida (Phaeophyta) , 2006, Journal of Applied Phycology.

[44]  J. Kamerling,et al.  Characterization by gas-liquid chromatography-mass spectrometry and proton-magnetic-resonance spectroscopy of pertrimethylsilyl methyl glycosides obtained in the methanolysis of glycoproteins and glycopeptides. , 1975, The Biochemical journal.

[45]  A. Varenne,et al.  Regioselective desulfation of sulfated L-fucopyranoside by a new sulfoesterase from the marine mollusk Pecten maximus: application to the structural study of algal fucoidan (Ascophyllum nodosum). , 2001, European journal of biochemistry.

[46]  B. Mulloy,et al.  Structure and Anticoagulant Activity of Sulfated Fucans , 1999, The Journal of Biological Chemistry.

[47]  S. Cui,et al.  Antitumor polysaccharides from mushrooms: a review on their isolation process, structural characteristics and antitumor activity , 2007 .

[48]  S. Turgeon,et al.  Characterization of polysaccharides extracted from brown seaweeds , 2007 .

[49]  I. Bakunina,et al.  Structure, biological activity, and enzymatic transformation of fucoidans from the brown seaweeds , 2008, Biotechnology journal.

[50]  R. D. Paula,et al.  Isolation and characterization of soluble sulfated polysaccharide from the red seaweed Gracilaria cornea , 2002 .

[51]  Alejandro Cifuentes,et al.  In the search of new functional food ingredients from algae , 2008 .

[52]  C. Hellerqvist Linkage analysis using Lindberg method. , 1990, Methods in enzymology.