PREPARATION AND STRUCTURE OF FIVE DERIVATIVES OF β-(1→3)-D-GLUCAN ISOLATED FROM PORIA COCOS SCLEROTIUM  

作　　者：张俐娜 

机构地区：[1]Department of Chemistry, Wuhan University, Wuhan 430072, China

出　　处：《Chinese Journal of Polymer Science》2004年第2期137-145,共9页高分子科学（英文版）

基　　金：This work was supported by the National Natural Science Foundation of China (No. 20074025), the Area of Excellence(AoE) on Plant and Fungal Biotechnology Project of the Hong Kong SAR Government and Key Laboratory of Cellulose andLignocellulosic Chemistry of Chinese Academy of Sciences.

摘　　要：A new solvent of cellulose (1.5 mol/L NaOH/0.5 mol/L urea aqueous solution) was used as one of the homogeneous reaction media of polysaccharides for methylation, hydroxyethylation and hydroxypropylation. A water insoluble β -(1—>3)-D-glucan, sample PCS3- isolated from fresh sclerotium of Poria cocos was sulfated in dimethyl sulfoxide (Me 2 SO), carboxymethylated in NaOH, isopropanol solution, as well as methylated, hydroxyethylated and hydroxypropylated in the new solvent system, respectively, to obtain five water-soluble derivatives coded as S-PCS3- C- PCS3- M-PCS3- HE-PCS3- and HP-PCS3- Their chemical structure and distribution of substitution were characterized by infrared spectroscopy (IR), elementary analysis (EA), 1 H-NMR, 13 C-NMR, 2D-COSY, 2D-TOCSY and 2D- 1 H-detected 1H 13C HMQC spectra. The results reveal that the relative reactivity of hydroxyl groups of the β -(1-?3)-D-glucan is in the order C-6 > C-4 > C-2 on the whole. The substitution of the samples S-PCS3- C-PCS3- and M-PCS3- occurred mainly at C-6 position and secondly at C-4 and C-2 positions, and that of HE-PCS3- occurred at C-6 and C-4 positions and of HP-PCS3- almost completely occurred at C-6 position. The degrees of substitution (DS) obtained from 13 C-NMR range from 0.23 to 1.27. The water solubility of the derivatives is in the order S-PCS3- >C-PCS3- >M-PCS3- >HE-PCS3- >HP-PCS3- This work provides a novel and nonpolluting process for the methylation, hydroxyethylation and hydroxypropylation of β -(1—>3)-D-glucan.A new solvent of cellulose (1.5 mol/L NaOH/0.5 mol/L urea aqueous solution) was used as one of the homogeneous reaction media of polysaccharides for methylation, hydroxyethylation and hydroxypropylation. A water insoluble β -(1—>3)-D-glucan, sample PCS3- isolated from fresh sclerotium of Poria cocos was sulfated in dimethyl sulfoxide (Me 2 SO), carboxymethylated in NaOH, isopropanol solution, as well as methylated, hydroxyethylated and hydroxypropylated in the new solvent system, respectively, to obtain five water-soluble derivatives coded as S-PCS3- C- PCS3- M-PCS3- HE-PCS3- and HP-PCS3- Their chemical structure and distribution of substitution were characterized by infrared spectroscopy (IR), elementary analysis (EA), 1 H-NMR, 13 C-NMR, 2D-COSY, 2D-TOCSY and 2D- 1 H-detected 1H 13C HMQC spectra. The results reveal that the relative reactivity of hydroxyl groups of the β -(1-?3)-D-glucan is in the order C-6 > C-4 > C-2 on the whole. The substitution of the samples S-PCS3- C-PCS3- and M-PCS3- occurred mainly at C-6 position and secondly at C-4 and C-2 positions, and that of HE-PCS3- occurred at C-6 and C-4 positions and of HP-PCS3- almost completely occurred at C-6 position. The degrees of substitution (DS) obtained from 13 C-NMR range from 0.23 to 1.27. The water solubility of the derivatives is in the order S-PCS3- >C-PCS3- >M-PCS3- >HE-PCS3- >HP-PCS3- This work provides a novel and nonpolluting process for the methylation, hydroxyethylation and hydroxypropylation of β -(1—>3)-D-glucan.

关 键 词：Chemical structure SULFATION CARBOXYMETHYLATION METHYLATION Hydroxyethylation HYDROXYPROPYLATION β-D- glucan Poria cocos sclerotium NMR 

分 类 号：O636.1[理学—高分子化学]