초록
tragacanth gum의 화학구조(化學構造)를 구명(究明)하기 위(爲)하여 미국(美國) 약전(藥典)의 tragacanth gum 분말(粉末)을 가지고 다음의 실험(實驗)을 통(通)하여 이의 성분(成分)의 하나인 polysaccharide C를 분리(分離)하여 이의 화학구조(化學構造)를 밝혔다. (1) tragacanth gum을 85% 주정(酒精)으로 처리(處理)해서 중성다당류(中性多糖類)로 polysaccharide C를 분리(分離)하였으며 구성당(構成糖)으로 L-rhamnose, D-xylose, L-arabinose 및 D-galactose를 paper chromatography와 Cellulose column chromatography로 분리(分離), 동정(同定)하였다. 이의 molar ratio는 2:1:17:9이며 비선광도(比旋光度)는 $[{\alpha}]^{30}_D-72.2이다. (2) 구성당(構成糖)의 결합위치(結合位置)를 구명(究明)하기 위(爲)해 Hawarth 법(法)과 Purdietldir(試藥)을 가지고 methyl화(化)시켜 methyl화(化) polysaccharide C를 얻었으며 비선광도(比旋光度) $[{\alpha}]^{22}_D-102를 보였다. 이것을 가수분해(加水分解)시켜 paper chromatography와 column chromatography를 통(通)해 methyl화단당(化單糖)으로 1,3,5-tri-O-methyl-L-arabofuranose, 3,4-di-O-methyl-L-rhamnose, 2,3-di-O-methyl-D-xylose, 2,3,4-tri-O-methyl-D-galactopyranose, 2,4-di-O-methyl-L-arabopyronose, 2,4-di-O-methyl-D-galactose, 2-O-methyl-L-arabinose 및 L-arabinose를 분리(分離), 동정(同定)하였다. (3) 산(酸)의 각종농도(各種濃度)에 따른 부분적(部分的) 가수분해(加水分解)를 시켜 polysaccharide C의 end group, 측지(側枝) 또는 주쇄(主鎖)를 이루는 구성당(構成糖)을 밝히기 위(爲)하여 0.05 N-HCl로 제1차(第一次) 가수분해(加水分解). 0.1N-HCl로 제2차(第二次) 가수분해(加水分解), 0.3N-HCl로 제3차(第三次) 가수분해(加水分解)를 하여 가수분해물(加水分解物)과 비가수분해물(非加水分解物)에서 각각(各各) 다음과 같은 구성단당(構成單糖)을 검출(檢出)하고 이들의 molar ratio를 측정(測定)하였다. 제1차(第一次) 가수분해물(加水分解物)(A)에서 L-arbinose, 비가수분해물(非加水分解物)(A')에서 L-rhamnose, D-xylose, L-arabinose 및 D-galactose; 제2차(第二次) 가수분해물(加水分解物)(B)에서 L-arabinose와 D-galactose, 비가수분해물(非加水分解物)(B')에서 L-rhamnose, D-xylose, L-arabinose, 및 D-galactose; 제3차(第三次) 가수분해물(加水分解物)(C)에서 L-rhamnose, D-xylose, L-arabinose 및 D-galactose, 비가수분해물(非加水分解物)(C')에서 D-xylose와 D-galactose를 검출(檢出)하였다. (4) 구성당(構成糖)의 형태(形態)와 구조(構造)를 밝히기 위(爲)해 polysaccharide C에 대한 periodate산화(酸化) 실험(實驗)을 하여 $C_5H_8O_4$당(當) periodate의 소비(消費)와 formic acid의 생성량(生成量)을 측정(測定)하였는데 periodate의 소비량(消費量)은 1.23 mole, formic acid의 생성량(生成量)은 0.78 mole이다.
The polysaccharide C prepared from gum tragacanth powder (U. S. P. grade) by the precipitation method with 85% ethanol was a neutral polysaccharide, $[{\alpha}]^{30}_D-72.2$. The polysaccharide C consisted of L-rhamnose, D-xylose, L-arabinose and D-galactose in the molar ratio 2:1:17:9 (Table 1, 2, 3, ). The polysaccharide C was methylated with dimethylsulphate and 40% NaOH, and Purdies regent. The hydrolyzate of fully methlated product ($[{\alpha}]^{22}_D-102$ in chloroform, the methoxy content 40.6%) was composed of 2, 3, 5-tri-O-methyl-L-arabofuranose (I), 3,4-di-O-methyl-L-rhamnopyranose (II), 2,3-di-O-methyl-D-xylose (III), 2,3,4-tri-O-methyl-D-galactopyranose (IV), 2,4-di-O-methyl-L-arabopyranose (?), 2,4-di-O-methyl-D-galactose(VI), 2-O-methyl-D-arabinose (VII), and L-arabopyranose(VIII) (Table 4, 5, and Fig. 4). The first partial hydrolysis (A) of the polysaccharide C with 0.05N-HCl for 4.5 hours at $80-85^{\circ}C$ released only L-arabinose: the second hydrolysis (B) with 0.1N-HCl for 5 hours at $80-85^{\circ}C$, L-arabinose and D-galactose; and the third hydrolysis (C) with 0.3N-HCl at $90-95^{\circ}C$ in sealed tube, L-rhamnose, D-xylose, L-arabinose and D-galactose. From the unhydrolyzate A' were found L-rhamnose, D-xylose, L-arabinose, and D-galactose; from B' L-rhamnose, d-xylose, L-arabinose and D-galactose; and from C' D-xylose and D-galactose respectively (Table 6). The periodate consumption and formic acid production of the polysaccharide C were measured at various time intervals. After 120 hours periodat was consumed by 1.23 mole per $C_5H_8O_4$ and formic acid was produced 0.78 mole per $C_5H_8O_4$ (Table 7). Although a definite chemical structure for this polysaccharide C may not be formulated, experimental data, especially, from methylation, partial hydrolysie and determination of its molar ratio, and periodate analysis showed that the polysaccharide C is a highly branched polysaccharide and would be constructed of galactoaraban as a main chain residue and L-arabofuranose, D-galactopyranosyl $(1{\rightarrow}1)$-L-arabofuranose, D-xylopyranosyl $(1{\rightarrow}2)$-L-rhamnopyranosyl $(1{\rightarrow}1)$-L-arabofuranose, and L-rhamnopyranosyl $(1{\rightarrow}1)$-arabofuranose, and D-galactopyranosyl-$(1{\rightarrow}2)$-L-arabopyranosyl-$(1{\rightarrow}1)$-I-arabofuranose as a branch chain or end group (page 21).