Studies on the dehydrogenative polymerization of monolignol β-glycosides. Part 6: Monitoring of horseradish peroxidase-catalyzed polymerization of monolignol glycosides by GPC-PDA
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Yuki Tobimatsu
Abstract
Horseradish peroxidase (HRP)-catalyzed dehydrogenative polymerization of guaiacyl (G) and syringyl (S)-type monolignol γ-O-glucosides, isoconiferin (iso-G) and isosyringin (iso-S), which contain a hydrophilic glucosyl unit on γ-position of coniferyl alcohol and sinapyl alcohol, respectively, was monitored by gel permeation chromatography coupled with photodiode array detection (GPC-PDA). Contrary to the conventional dehydrogenative polymerization of monolignols, the polymerization of the glycosides produces water-soluble synthetic lignins (DHPs) in a homogeneous aqueous phase. Taking advantage of this unique reaction system, the method was developed to follow the changes of molecular weights in the course of DHP formations. Moreover, PDA detection permits determination of oligomeric S-type quinone methide intermediates (QMs) formed as stable transient compounds during polymerization of iso-S. A detailed comparison of the polymerization profiles revealed entirely different behaviors of G- and S-type monomers. The data strongly support the view that the low reactivity of oligomeric S-type QMs impedes the formation of DHPs from S-type monomers. In copolymerization of G- and S-type monomers, it is conceivable that G-type phenolic hydroxyl groups serve as good nucleophilic reactants to scavenge S-type QMs resulting in efficient production of DHPs. As a consequence, the present approach can be a powerful tool to study the in vitro dehydrogenative polymerization providing further mechanistic insights into lignin polymerization in vivo.
©2010 by Walter de Gruyter Berlin New York
Artikel in diesem Heft
- Original Papers
- Recombinant manganese peroxidase (rMnP) from Pichia pastoris. Part 1: Kraft pulp delignification
- Recombinant manganese peroxidase (rMnP) from Pichia pastoris. Part 2: Application in TCF and ECF bleaching
- The role of hydroxyl and oxyl anion radicals in selectivity of oxygen delignification
- Thermal aging of 1-alkyl-3-methylimidazolium ionic liquids and its effect on dissolved cellulose
- Synchrotron X-ray fiber diffraction study on the thermal expansion behavior of cellulose crystals in tension wood of Japanese poplar in the low-temperature region
- Studies on the dehydrogenative polymerization of monolignol β-glycosides. Part 6: Monitoring of horseradish peroxidase-catalyzed polymerization of monolignol glycosides by GPC-PDA
- Reactivity of syringyl quinone methide intermediates in dehydrogenative polymerization. Part 2: pH effect in horseradish peroxidase-catalyzed polymerization of sinapyl alcohol
- Fractionation, analysis, and PCA modeling of properties of four technical lignins for prediction of their application potential in binders
- New model for predicting tensile strength and density of eucalyptus handsheets based on an activation parameter calculated from fiber distribution characteristics
- Extractives of the tropical wood wallaba (Eperua falcata Aubl.) as natural anti-swelling agents
- Surface properties of extracts from cork black condensate
- Effect of helium DBD plasma treatment on the surface of wood samples
- Preparation of thermoplastic molding from steamed Japanese beech flour
- Alteration of the unsteady sorption behaviour of maple (Acer pseudoplatanus L.) and spruce (Picea abies (L.) Karst.) due to thermal modification
- Towards improved understanding of PEG-impregnated waterlogged archaeological wood: A model study on recent oak
- Determination of the change in appearance of lumber surfaces illuminated from various directions
- A study of water exchange in wood by means of 2D NMR relaxation correlation and exchange
- Measurement of surface growth stress in Eucalyptus nitens Maiden by splitting a log along its axis
- Obituary
- Dion Chen-Loung Chen (1930–2009)
- Meetings
- Meetings
Artikel in diesem Heft
- Original Papers
- Recombinant manganese peroxidase (rMnP) from Pichia pastoris. Part 1: Kraft pulp delignification
- Recombinant manganese peroxidase (rMnP) from Pichia pastoris. Part 2: Application in TCF and ECF bleaching
- The role of hydroxyl and oxyl anion radicals in selectivity of oxygen delignification
- Thermal aging of 1-alkyl-3-methylimidazolium ionic liquids and its effect on dissolved cellulose
- Synchrotron X-ray fiber diffraction study on the thermal expansion behavior of cellulose crystals in tension wood of Japanese poplar in the low-temperature region
- Studies on the dehydrogenative polymerization of monolignol β-glycosides. Part 6: Monitoring of horseradish peroxidase-catalyzed polymerization of monolignol glycosides by GPC-PDA
- Reactivity of syringyl quinone methide intermediates in dehydrogenative polymerization. Part 2: pH effect in horseradish peroxidase-catalyzed polymerization of sinapyl alcohol
- Fractionation, analysis, and PCA modeling of properties of four technical lignins for prediction of their application potential in binders
- New model for predicting tensile strength and density of eucalyptus handsheets based on an activation parameter calculated from fiber distribution characteristics
- Extractives of the tropical wood wallaba (Eperua falcata Aubl.) as natural anti-swelling agents
- Surface properties of extracts from cork black condensate
- Effect of helium DBD plasma treatment on the surface of wood samples
- Preparation of thermoplastic molding from steamed Japanese beech flour
- Alteration of the unsteady sorption behaviour of maple (Acer pseudoplatanus L.) and spruce (Picea abies (L.) Karst.) due to thermal modification
- Towards improved understanding of PEG-impregnated waterlogged archaeological wood: A model study on recent oak
- Determination of the change in appearance of lumber surfaces illuminated from various directions
- A study of water exchange in wood by means of 2D NMR relaxation correlation and exchange
- Measurement of surface growth stress in Eucalyptus nitens Maiden by splitting a log along its axis
- Obituary
- Dion Chen-Loung Chen (1930–2009)
- Meetings
- Meetings
