Synthetic dehydropolymerizates

Synthetic dehydropolymerizates (DHPs, so called “lignin-like”) can be obtained by H2O2/peroxidase catalyzed one-electron oxidation of monolignols. While generating some of the substructures found in native lignins, there is, of course, little opportunity for control over primary chain interunit linkage (sequence) designation with in vitro preparations. Thus, numerous important differences between synthetic DHPs [which, for example, re­lease dimeric pinoresinol-derived substructures (see Figure 7.2D, substructure Illb) upon cleavage] and native lignin polymers [which do not(193)] have long been known, and which diminish greatly their utility (29). While it is possible to synthesize 8- O-4′ linked oligomers (194), and also to modulate the amounts of 8-O-4′ interunit linkages through varying peroxidase activity in vitro (195), such preparations are not lignins proper. Indeed, in many respects, the comparison of synthetic DHPs to native lignins might be likened to that of randomly linking amino acids through amide linkages in the same relative proportions as found in insulin, and describing the resulting products as an insulin mimic.