Investigation on the hydrogen abstraction from methyl glucoside by active oxygen species under oxygen delignification conditions IV: Appearance of kinetic isotope effect in the reaction between methyl glucoside and deuterated methyl glucoside
2012
Nakagawa, A. (The University of Tokyo, Bunkyo-ku, Tokyo (Japan). Graduate School of Agricultural and Life Sciences, Department of Biomaterial Sciences, Laboratory of Wood Chemistry) | Yokoyama, T. | Matsumoto, Y.
In our previous studies, a clear kinetic isotope effect was observed when a pair of carbohydrate model compounds, methyl beta-d-glucopyranoside (MGPbeta) and a deuterated MGPbeta labeled at the anomeric (methyl beta-D-(1-sup(2)H)glucopyranoside) or C-2 position (methyl beta-D-(2-sup(2)H)glucopyranoside), was reacted with active oxygen species (AOS) generated by reactions between O2 and a phenolic compound, 2,4,6-trimethylphenol (TMPh), under oxygen delignification conditions. These results indicate that the AOS abstract the anomeric and C-2 hydrogens of MGPbeta. Contrarily, no clear kinetic isotope effects were observed when AOS were generated by reactions between O2 and another phenolic compound, 4-hydroxy-3-methoxybenzyl alcohol (vanillyl alcohol, Valc), and hence, the abstraction of the anomeric and C-2 hydrogens by the AOS was not confirmed. In this study, a pair of MGPbeta and the deuterated MGPbeta labeled at all the positions, (sup(2)Hsub(3))methyl beta-D-(1,2,3,4,5,6,6-sup(2)Hsub(7))glucopyranoside, was reacted with AOS generated from TMPh or Valc under oxygen delignification conditions to further examine the appearance of a kinetic isotope effect. A clear kinetic isotope effect was observed when either of TMPh or Valc was the origin of AOS, indicating that some AOS abstract at least a hydrogen of MGPbeta in either case. The results are further discussed focusing on the type of AOS generated from TMPh and Valc.
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