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Title: 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
Authors: Tobimatsu, Yuki  kyouindb  KAKEN_id  orcid (unconfirmed)
Takano, Toshiyuki  kyouindb  KAKEN_id
Kamitakahara, Hiroshi  kyouindb  KAKEN_id  orcid (unconfirmed)
Nakatsubo, Fumiaki
Author's alias: 高野, 俊幸
Keywords: Dehydrogenation polymer (DHP)
Horseradish peroxidase (HRP)
Nucleophilic addition
Quinone methide
Syringyl lignin
Issue Date: Jun-2010
Publisher: Springer
Journal title: Journal of Wood Science
Volume: 56
Issue: 3
Start page: 233
End page: 241
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.
Rights: The original publication is available at
This is not the published version. Please cite only the published version. この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。
DOI(Published Version): 10.1007/s10086-009-1086-5
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