Structural characterization of hemicelluloses fractionated by graded ethanol precipitation from Pinus yunnanensis

Abstract

Fractionation of hemicelluloses from delignified Pinus yunnanensis was carried out with KOH/H3BO3 solution followed by graded precipitation in 15%, 60%, and 90% (v/v) ethanol solutions, respectively. Chemical compositions, physicochemical properties, and structures of the precipitated hemicellulosic fractions were elucidated by a combination of sugar analysis, GPC, FT-IR, and 1H, 13C and 2D HSQC NMR spectroscopy. Sugar analysis showed that the hemicellulosic fraction precipitated by 15% ethanol solution (H1) had a predominance of xylose (58.52%), while mannose was the major sugar component in the hemicellulosic fractions precipitated by 60% (H2) and 90% (H3) ethanol solutions. GPC results revealed that the hemicelluloses precipitated by low concentration of ethanol solutions had higher weight-average molecular mass (50,090–79,840g/mol) than those obtained in the high concentration of ethanol solutions (16,500g/mol). The fraction precipitated by 60% ethanol solution (H2) was composed of d-galactose, d-glucose and d-mannose in a ratio of approximately 1:1:3.5. Structural determination indicated that the hemicellulosic fraction (H2) had a main structure of (1→4)-linked β-glucomannans backbone with (1→6)-linked α-d-galactose as a side chain attached to C-6 of mannose units. In addition, this fraction also contained minor amounts of xylans.