Investigation of a sulfate transfer during autohydrolysis of a fucoidan from the brown alga Fucus evanescens by tandem ESIMS

A fucoidan from the brown alga Fucus evanescens was effectively depolymerized by autohydrolysis. Negative-ion electrospray ionization mass spectrometry (ESIMS) revealed that the mixture contained sulfated mono- and oligosaccharides with polymerization degree (DP) up to 6, having from 1 to 4 sulfate groups per molecule. The prevalence of oligosaccharides with even DP was observed. It could be explained by the tendency of the 3-linked α-l-fucopyranose residues to hydrolyze faster than 4-linked ones. The intermolecular sulfate transfer during autohydrolysis was detected by ESIMS, when equimolar quantities of d-Rib and d-Glc were added as acceptors. The products were singly-sulfated and hexose was about four times more effective as an acceptor, than pentose. It was impossible to record MS/MS spectra of the sulfate transfer products, since intensities of their ions were too low.