Synthesis, (1 → 3)-β- D-glucanase-binding ability, and phytoalexin-elicitor activity of a mixture of 3,4-epoxybutyl (1 → 3)-β- D-oligoglucosides

Abstract

We describe a approach for the synthesis of a mixture of 3,4-epoxybutyl (1 → 3)-β- D-oligoglucosides. The particular (1 → 3)-β- D-glucan isolated from the cell walls of Saccharomyces cerevisiae was recovered from the aqueous medium as water-insoluble particles by the spray drying (GS) method, and it was characterized by FTIR spectroscopy. The acid-solubilized (1 → 3)-β- D-oligoglucosides were prepared by partial acid hydrolysis of glucan particles, which were qualitatively analyzed by fluorophore-assisted carbohydrate electrophoresis (FACE). The peracetylated 3-butenyl (1 → 3)-β- D-oligoglucosides were synthesized by treating peracetylated (1 → 3)-β- D-oligoglucosides with the 3-butenyl alcohols and a Lewis acid (SnCl 4) catalyst. Epoxidation of the peracetylated 3-butenyl oligoglucosides took place with m-chloroperoxybenzoic acid ( m-CPBA). NaOMe in dry methanol was used for the deacetylation of the blocked derivatives, to give the 3,4-epoxybutyl (1 → 3)-β- D-oligoglucoside mixture in an overall yield of 21%. The sample was analyzed by positive-ion electrospray ionization mass spectrometry (ESIMS). In a 3,4-epoxybutyl (1 → 3)-β- D-oligoglucoside-binding (1 → 3)-β- D-glucanase assay, we found that the (1 → 3)-β- D-glucanase was obviously inactivated by the 3,4-epoxybutyl (1 → 3)-β- D-oligoglucosides. At the same time, we found the 3,4-epoxybutyl (1 → 3)-β- D-oligoglucoside mixture was more active as compared to the underivatized oligoglucoside mixture in eliciting phytoalexin accumulation in tobacco cotyledon tissue. Furthermore, it could be kept for a longer time than a (1 → 3)-β- D-oligoglucoside mixture, which indicated it is much more stable than (1 → 3)-β- D-oligoglucosides.