Determination of Arylglycerol−β-Aryl Ether Linkages in Enzymatic Mild Acidolysis Lignins (EMAL): Comparison of DFRC/31P NMR with Thioacidolysis⊥

Enzymatic mild acidolysis lignins (EMAL) isolated from different species of softwood and Eucalyptus globulus were submitted to comparative analysis that included thioacidolysis, derivatization followed by reductive cleavage (DFRC), and DFRC followed by quantitative 31 P NMR (DFRC/ 31 P NMR). While gas chromatography (GC) was used to determine the monomer yields from both thioacidolysis and DFRC, 31 P NMR studies quantified the various phenolic hydroxy groups released by DFRC. The monomer yields from thioacidolysis and DFRC were substantially different, with thioacidolysis resulting in higher yields. In contrast, an excellent agreement was obtained in the total number of β-aryl ether structures determined by thioacidolysis and DFRC/ 31 P NMR, indicating that the combination of DFRC with quantitative 31 P NMR overcomes, at least in part, the limitations presented by the DFRC method. Both thioacidolysis and DFRC/ 31 P NMR were further used to better understand the lignin isolation process from wood. The results show that mild rotary ball milling minimizes, but does not prevent, the degradation of β-O-4 structures during the early stages of wood pulverization. The extent of such degradation was found to be higher for E. globulus than for a variety of softwoods examined. Furthermore, the structures of the EMALs isolated at yields ranging from 20% to 62% were very similar, indicating structural homogeneity in the lignin biopolymer within the secondary wall.