Abstract

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.

Highlights

  • The photocatalytic degradation reaction was optimized by varying the illumination time and the addition amount of TiO2 and H2 O2

  • The results show that the photocatalytic degradation method could improve the degradation efficiency of fucoidan

  • The photocatalytic degradation reaction condition was optimized to obtain lowmolecular-weight fucoidans by varying the illumination time and the addition amounts of TiO2 and H2 O2

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Summary

Introduction

Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. Acid hydrolysis has often been applied to degrade polysaccharides, but it could cause environmental pollution. It could damage the sulfate group of fucoidan leading to the loss of bioactivity [16]. It is necessary to find an environmentally friendly, low-cost, high-efficiency degradation method which can retain the sulfate group of fucoidan. Photochemical oxidation processes have been used for degradation of many different organic pollutants [20] This process is simpler, higher yielding and more environmentally benign than conventional methods. The photons with a higher energy than the band gap can be absorbed while an electron is promoted to the conduction band, leaving a hole in the valence band This excited electron can be used to drive a degradation reaction [21]. The present study investigated the TiO2 -catalyzed photocatalytic reaction for fucoidan degradation, and the degradation products were characterized and compared with the undegraded fucoidan by a series of analysis techniques to reveal the compositional, structural, cytotoxicity and anticoagulant activity changes of polysaccharides caused by photocatalytic degradation

Materials
Photocatalytic Degradation of Fucoidan
Chemical Analysis
Determination of Molecular Weight Distribution
Thin Layer Chromatography (TLC)
Analysis of Monosaccharide Composition
Fourier-Transform Infrared (FT-IR) Spectroscopic Analysis
Mass Spectrometry Analysis
Anticoagulant
2.11. Cytotoxicity
2.12. Chromogenic Factor XII Activation Assay
Optimization of Photocatalytic Degradation Conditions
OH and as illuminated in
Chemical Composition Analysis
Identification of Oligosaccharides by Photocatalytic
Cytotoxicity the Degraded
Cytotoxicity of the Degraded Fucoidans
Effects
Conclusions
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