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Journal of Wood Science

Official Journal of the Japan Wood Research Society

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Reactivity of syringyl quinone methide intermediates in dehydrogenative polymerization I: high-yield production of synthetic lignins (DHPs) in horseradish peroxidase-catalyzed polymerization of sinapyl alcohol in the presence of nucleophilic reagents

Journal of Wood Science volume 56, pages 233–241 (2010)Cite this article

Abstract

It is known that the conventional dehydrogenative polymerization of sinapyl alcohol (S-alc) gave syringyl synthetic lignins (S-DHPs), but in extremely low yields. In this article, to examine the contribution of syringyl quinone methide intermediates (S-QM) on S-DHP production, horseradish peroxidase (HRP)-catalyzed dehydrogenative polymerization of S-alc was carried out in the presence of nucleophilic reagents that promote the rearomatization of S-QM. First, the HRP-catalyzed polymerization of sinapyl alcohol γ-O-β-D-glucopyranoside (isosyringin, iso-S), which allows us to monitor the polymerization process in a homogeneous aqueous phase, was utilized for screening of a nucleophile used as an S-QM scavenger. Monitoring of iso-S polymerization in the presence of various nucleophilic reagents by UV spectroscopy and gel permeation chromatography with photodiode array detection (GPC-PDA) revealed a high ability of azide ion to convert oligomeric S-QM efficiently to S-DHP. Accordingly, azide ion was utilized as an S-QM scavenger in HRP-catalyzed polymerization of S-alc, which resulted in high-yield production of S-DHPs (∼83%), as expected. The 1H-, 13C-, and 2D-HSQC NMR investigations on the resulting S-DHPs clearly demonstrated that azide ion efficiently performed nucleophilic additions to the C-α of S-QM during the polymerization. These results provide experimental proof that the low reactivity of S-QM with nucleophiles (such as water, phenolic, and aliphatic hydroxyl groups) in the conventional polymerization system critically impedes the production of S-DHPs from S-alc.

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Authors and Affiliations

  1. Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Kitashirakawaoiwake-cho, Sakyo-ku, Kyoto, 606-8502, Japan

    Yuki Tobimatsu, Toshiyuki Takano, Hiroshi Kamitakahara & Fumiaki Nakatsubo

Authors
  1. Yuki Tobimatsu
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  2. Toshiyuki Takano
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  3. Hiroshi Kamitakahara
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  4. Fumiaki Nakatsubo
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Correspondence to Toshiyuki Takano.

Additional information

This report follows the previous rapid communication “Azide ion as a quinone methide scavenger in the horseradish peroxidase-catalyzed polymerization of sinapyl alcohol”, J Wood Sci (2008) 54:87–89

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Tobimatsu, Y., Takano, T., Kamitakahara, H. et al. Reactivity of syringyl quinone methide intermediates in dehydrogenative polymerization I: high-yield production of synthetic lignins (DHPs) in horseradish peroxidase-catalyzed polymerization of sinapyl alcohol in the presence of nucleophilic reagents. J Wood Sci 56, 233–241 (2010). https://doi.org/10.1007/s10086-009-1086-5

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  • DOI: https://doi.org/10.1007/s10086-009-1086-5

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