Methyl-esterification, degree of polymerization and ∆4,5-unsaturation of galacturonic acid oligosaccharides as determinants of immunomodulation

Carbohydr Polym. 2025 Feb 15:350:123052. doi: 10.1016/j.carbpol.2024.123052. Epub 2024 Nov 22.

Abstract

In recent years, immunomodulation by pectin and pectin-derived galacturonic acid oligosaccharides has been the subject of wide-spread scientific research due to the potential of different pectin structures as bioactive biomolecules. Yet, gaps remain in understanding the structure-dependent immunomodulation of galacturonic acid. This study describes in vitro immunomodulatory effects of well-characterized galacturonic acid oligosaccharides. Both methyl-esterified and non-methyl-esterified galacturonic acid oligosaccharides with a saturated non-reducing end (degree of polymerization 1-10) significantly induced cytokine production by THP-1 macrophages and directly activated TLR2 and TLR4 in transfected HEK-293 cells, even when accounting for minor endotoxin contamination. In contrast, both methyl-esterified and non-methyl-esterified galacturonic acid oligosaccharides with a Δ4,5-unsaturated non-reducing end (degree of polymerization 1-7) did not activate TLR2 and TLR4 and led to significantly reduced cytokine production (p < 0.05), suggesting Δ4,5-(un)saturation as a pivotal factor for immunomodulation by galacturonic acid oligosaccharides. Exposure to non-methyl-esterified saturated galacturonic acid oligosaccharides resulted in significantly lower TNF-α production, IL-1β production and TLR4 activation (p < 0.05) compared to methyl-esterified saturated galacturonic acid oligosaccharides, while IL-10 production and TLR2 activation remained unchanged. These findings establish galacturonic acid oligosaccharides as versatile immunomodulators with TLR2 and TLR4 binding capacity, fit for different immunomodulatory applications depending on their structural characteristics.

Keywords: Galacturonic acid; Immunomodulation; Methyl-esterification; Pattern recognition receptors; Pectin.

MeSH terms

  • Cytokines / metabolism
  • Esterification
  • HEK293 Cells
  • Hexuronic Acids* / chemistry
  • Hexuronic Acids* / pharmacology
  • Humans
  • Immunomodulation / drug effects
  • Macrophages / drug effects
  • Macrophages / immunology
  • Macrophages / metabolism
  • Oligosaccharides* / chemistry
  • Oligosaccharides* / pharmacology
  • Pectins / chemistry
  • Pectins / pharmacology
  • Polymerization*
  • THP-1 Cells
  • Toll-Like Receptor 2* / metabolism
  • Toll-Like Receptor 4* / metabolism

Substances

  • galacturonic acid
  • Oligosaccharides
  • Hexuronic Acids
  • Toll-Like Receptor 4
  • Toll-Like Receptor 2
  • TLR4 protein, human
  • TLR2 protein, human
  • Cytokines
  • Pectins