It is a challenge to degrade sulfated polysaccharides without stripping sulfate groups. In the present study, a photocatalytic method was applied to degrade fucoidan, a sulfated polysaccharide from brown algae. The degradation with varying addition amounts of H₂O₂ and TiO₂ were monitored by high performance gel permeation chromatography (HPGPC) and thin layer chromatography (TLC), and fucoidan was efficiently degraded with 5% TiO₂ and 0.95% H₂O₂. A comparison of the chemical compositions of 2 products obtained after 0.5 h and 3 h illumination, DF-0.5 (average Mw 90 kDa) and DF-3 (average Mw 3 kDa), respectively, with those of fucoidan indicates the photocatalytic degradation did not strip the sulfate groups, but reduced the galactose/fucose ratio. Moreover, 12 oligosaccharides in DF-3 were identified by HPLC-ESI-MSⁿ and 10 of them were sulfated. In addition, DF-0.5 showed anticoagulant activity as strong as fucoidan while DF-3 could specifically prolong the activated partial thromboplastin time. All samples exerted inhibition effects on the intrinsic pathway FXII in a dose-dependent manner. Thus, photocatalytic degradation demonstrated the potential to prepare sulfated low-molecular-weight fucoidan with anticoagulant activity.

The present study aimed to clarify the potential mechanism of fucoidans found in Ascophyllum nodosum on anti-inflammation and to further explore the relationship between their structures and anti-inflammation. Two novel fucoidans named ANP-6 and ANP-7 and found in A. nodosum, were separated and purified and their structures were elucidated by HPGPC, HPLC, GC-MS, FT-IR, NMR, and by the Congo red test. They both possessed a backbone constructed of →2)-α-L-Fucp4S-(1→, →3)-α-L-Fucp2S4S-(1→, →6)-β-D-Galp-(1→, and →3,6)-β-D-Galp4S-(1→ with branches of →2)-α-L-Fucp4S-(1→ and →3)-β-D-Galp-(1→. Moreover, ANP-6 and ANP-7 could prevent the inflammation of the LPS-stimulated macrophages by suppressing the NO production and by regulating the expressions of iNOS, COX-2, TNF-α, IL-1β, IL-6, and IL-10. Their inhibitory effects on the TLR-2 and TLR-4 levels suggest that they inhibit the inflammation process via the blocking of the TLR/NF-κB signal transduction. In addition, ANP-6, with a molecular weight (63.2 kDa), exhibited stronger anti-inflammatory capabilities than ANP-7 (124.5 kDa), thereby indicating that the molecular weight has an influence on the anti-inflammatory effects of fucoidans.