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Regioselective modification is an effective approach to synthesize polysaccharides with different structure features and improved properties. In this study, regioselective sulfation of Artemisia sphaerocephala polysaccharide (S RS ASP) was prepared by using triphenylchloromethane (TrCl) as protecting precursor. The decrease in fractal dimension ( d f ) values (1.56–2.04) of S RS ASP was observed in size-exclusion chromatography combined with multi angle laser light scattering (SEC-MALLS) analysis. Compared to sample substituted at C-6, S RS ASP showed a more expanded conformation of random coil, which was attributed to the breakup of hydrogen bonds and elastic contributions. Circular dichroism (CD), methylene blue (MB) and congo red (CR) spectrophotometric method and atomic force microscopy (AFM) results confirmed the conformational transition and stiffness of the chains after sulfation. S RS ASP exhibited enhanced antioxidant activities in the DPPH, superoxide and hydroxyl radical scavenging assay. Sulfation at C-2 or C-3 was favorable for the chelation which might prevent the generation of hydroxyl radicals. It concluded that the degree of substitution and substitution position were the factors influencing biological activities of sulfated polysaccharides. [ABSTRACT FROM AUTHOR]

Abstract: We reported here a regioselective synthesis of non-C-6 phosphorylated guar gum (PRSGG) with a degree of substitution (DS) 0.34. Triphenylchloromethane (TrCl) was employed as a key protected precursor. Detritylation was performed by treatment with an excess of dichloroacetic acid. Phosphorylated GG was successfully characterized by FT-IR and 13C NMR spectroscopies. It was indicated that C-2 and C-3 substitution was predominant in phosphorylated polysaccharide. A decrease in weight average molar mass (M w) was observed in the reaction due to the acid environment in deprotection procedure. The results of vitro antioxidant experiments revealed that regioselective phosphorylation at C-2/C-3 and low M w afforded strong antioxidant activities. Non-C-6 phosphorylated guar gum showed a much higher scavenging abilities of 1,1-diphenyl-2-picrylhydrazyl (DPPH) and hydroxyl radical than C-6-phosphorylated derivative. [Copyright &y& Elsevier]

Abstract: We reported here a new synthesis of C-2 and C-3 sulfated guar gum (SRSGG) with low degree of substitution (DSS) of 0.58, employing triphenylchloromethane (TrCl) as a protected precursor. The yield and DSTr (calculated from the weight of triphenylmethanol) of triphenylmethylated GG (GGTr) was 165.6% and 0.71, respectively. In addition, low ratio (1:4) of chlorosulfuric acid to pyridine (1:4) was chosen in sulfation reaction since the protecting group was slightly sensitive to acid. Results of FT-IR and 13C NMR spectroscopy indicated that C-2 and C-3 substitution was predominant but not fully sulfated in SRSGG. Size-exclusion chromatograph combined with multi-angle laser photometer (SEC-LLS) showed a decrease in molecular weight in the reaction. This might be due to the degradation in sulfation and deprotection process. Finally, we investigated the effect of structure features on the antioxidant activities in vitro. Vitro antioxidant experiments revealed that the regioselective sulfation at C-2 and C-3 and low molecular weight afforded strong antioxidant activities showing a much higher scavenging abilities of 1,1-diphenyl-2-picrylhydrazyl (DPPH) and hydroxyl radical than that by the known C-6-sulfated derivative. The antioxidant activities of sulfated polysaccharides were not a function of a single factor but a combination of molecular weight, DSS and substitution positions. [Copyright &y& Elsevier]

Abstract: Selenium (Se) is an essential trace element for human beings and many other forms of life. Organic Se from natural foods has higher bioavailability and is safer than inorganic Se species. In the present study, selenium-containing derivatives of Artemisia sphaerocephala polysaccharide with the highest Se content of 1703μg/g were synthesized using H2SeO3/HNO3 and BaCl2 as a catalyst. The effects of the ratio of HNO3 concentration and reaction temperature were investigated. Results of Raman and 13C NMR spectroscopy indicated that C-6 substitution was predominant in selenized polysaccharide. A sharp decrease in M w was observed in the selenized reaction due to the acid environment. The in vitro antioxidant results suggest that selenium-containing polysaccharide should be applied as a novel selenium source in dietary supplements, with potent antioxidant properties. [Copyright &y& Elsevier]