Methanolysis of bark suberins: analysis of glycerol and acid monomers

The depolymerization and subsequent analysis of cork suberins from the outer barks of Pseudotsuga menziesii and Quercus suber was performed using a simplified methanolysis procedure. The amount of sodium methoxide catalyst was maintained at 20–30 mM and the methanolysis mixture was submitted to trimethylsilyl derivatisation and used directly for gas chromatographic analysis, allowing simultaneous quantification of glycerol and long-chain monomers. Response factors for glycerol, ferulic acid and one saturated homologue representing each of the suberinic families (i.e. the 1-alkanols, 1-alkanoic acids, ω-hydroxyacids and α,ω-diacids) were determined. Effective depolymerization of suberin was checked using the infrared specta of the residues after methanolysis. Glycerol is a major constituent of the suberins from P. menziesii (26% of total) and from Q. suber (14%). In both suberins, α,ω-diacids are dominant, i.e. 54% of the long-chain monomers in P. menziesii (mostly saturated C16-C22 homologues and the C18 unsaturated diacid), and 53% in Q. suber (mostly the C18 unsaturated diacid and mid-chain oxygenated (epoxide and vic-diol) derivatives). In P. menziesii epoxyacids are absent. The importance of glycerol and α,ω-diacids as suberin monomers supports a polymeric structure based on their successive esterification.