Polymerization of coniferyl alcohol by Mn3+-mediated (enzymatic) oxidation: Effects of H2O2 concentration, aqueous organic solvents, and pH

Roberto Taboada-Puig (Corresponding Author), Thelmo Lú-Chau, María Moreira, Gumersindo Feijoo, Juan Lema, Kurt Fagerstedt, Taina Ohra-aho, Tiina Liitiä, Harri Heikkinen, Jarmo Ropponen, Tarja Tamminen

Research output: Contribution to journalArticleScientificpeer-review


The objective of this study was to evaluate the ability of one versatile peroxidase and the biocatalytically generated complex Mn(III)-malonate to polymerize coniferyl alcohol (CA) to obtain dehydrogenation polymers (DHPs) and to characterize how closely the structures of the formed DHPs resemble native lignin. Hydrogen peroxide was used as oxidant and Mn2+ as mediator. Based on the yields of the polymerized product, it was concluded that the enzymatic reaction should be performed in aqueous solution without organic solvents at 4.5 ≤ pH ≤ 6.0 and with 0.75 ≤ H2O2:CA ratio ≤ 1. The results obtained from the Mn3+-malonate-mediated polymerization showed that the yield was almost 100%. Reaction conditions had, however, effect on the structures of the formed DHPs, as detected by size exclusion chromatography and pyrolysis-GC/MS. It can be concluded that from the structural point of view, the optimal pH for DHP formation using the presently studied system was 3 or 4.5. Low H2O2/CA ratio was beneficial to avoid oxidative side reactions. However, the high frequency of β–β linkages in all cases points to dimer formation between monomeric CA rather than endwise polymerization.
Original languageEnglish
Pages (from-to)81-90
Number of pages10
JournalBiotechnology Progress
Issue number1
Early online date10 Oct 2017
Publication statusPublished - 2018
MoE publication typeNot Eligible


  • bjerkandera sp
  • coniferyl alcohol
  • dehydrogenated polymer
  • Mn(III)-malonate
  • polymerization
  • versatile peroxidase

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