Controlled Non-Degradable Sulfation of Galactoglucomannan and the Effect of Modified Polysaccharides on Anticoagulant and Antioxidant Activity

The application of natural polysaccharides and their sulfated derivatives have already been successfully implemented in the pharmaceutical and food industries, in particular. The present study is concerned with modifying a predominant polysaccharide in the composition of spruce wood, galactoglucomannan (GGM), by sulfation via a urea-sulfamic acid complex in a 1,4-dioxane medium. By varying the sulfation process duration from 30 to 180 min, six novel GGM sulfate samples with different degrees of substitution (DS) of 0.4–1.2 were obtained and studied with a combination of modern physicochemical methods: elemental analysis, Fourier transform infrared (FTIR) spectroscopy, and gel permeation chromatography (GPC). It has been revealed that the sulfation of GGM proceeds without degradation of the main polymer chain, as evidenced by the shift in the main peak toward the high-molecular-weight region in the GPC curves. Moreover, modification of the polysaccharide leads to a significant transformation of the molecular conformation from a dense sphere to a random coil (α from 0.30 to 0.76). Furthermore, it has been determined that sulfate-substituted groups of the GGM tended to decrease the scavenging capacity of the 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radicals. However, the 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) assay showed an increase in the free radical inhibitory capacity of sulfated polysaccharides. This is attributed to the structural and conformational properties of the polysaccharide sulfate derivatives. The maximum anticoagulant activity (ACA) of sulfated GGM (SGGM) is 21.19 ± 2.89 IU/mg and increases with increasing sulfation duration.