Enzymatic Synthesis of 1,5-Anhydro-4- O-β-D-glucopyranosyl-D-fructose Using Cellobiose Phosphorylase and Its Spontaneous Decomposition via β-Elimination

Takahito Kajiki; Kazuhiro Yoshinaga; Shiro Komba; Motomitsu Kitaoka

doi:10.5458/jag.jag.JAG-2017_010

Enzymatic Synthesis of 1,5-Anhydro-4- O-β-D-glucopyranosyl-D-fructose Using Cellobiose Phosphorylase and Its Spontaneous Decomposition via β-Elimination

J Appl Glycosci (1999). 2017 Nov 20;64(4):91-97. doi: 10.5458/jag.jag.JAG-2017_010. eCollection 2017.

Authors

Takahito Kajiki^{1

2}, Kazuhiro Yoshinaga², Shiro Komba¹, Motomitsu Kitaoka¹

Affiliations

¹ 1 Food Research Institute, National Agriculture and Food Research Organization.
² 2 Sunus Co., Ltd.

Abstract

Cellobiose phosphorylase from Cellvibrio gilvus was used to prepare 1,5-anhydro-4-O-β-D-glucopyranosyl-D-fructose [βGlc(1→4)AF] from 1,5-anhydro-D-fructose and α-D-glucose 1-phosphate. βGlc(1→4)AF decomposed into D-glucose and ascopyrone T via β-elimination. Higher pH and temperature caused faster decomposition. However, decomposition proceeded significantly even under mild conditions. For instance, the half-life of βGlc(1→4)AF was 17 h at 30 °C and pH 7.0. Because βGlc(1→4)AF is a mimic of cellulose, in which the C2 hydroxyl group is oxidized, such decomposition may occur in oxidized cellulose in nature. Here we propose a possible oxidizing pathway by which this occurs.

Keywords: 1,5-anhydro-4-O-β-D-glucopyranosyl-D-fructose; 1,5-anhydro-D-fructose; ascopyrone; cellobiose phosphorylase; β-elimination.

2017 by The Japanese Society of Applied Glycoscience.