HEIDELBERGER M, TYLER J M, MUKHERJEE S
Immunology. 1962 Nov;5(6):666-72.
Although ketha gum has been reported to contain arabinose, galactose, xylose, an unidentified neutral sugar and glucuronic acid, its marked cross-reaction with Type I antipneumococcal horse sera led to the conclusion that D-galacturonic acid must be an additional component. The capsular polysaccharide of Type I pneumococcus, the determinant of immunological specificity, consists of more than 50 per cent of D-galacturonic acid. Chromatography of hydrolysates of ketha gum confirmed the presence of arabinose, galactose and xylose, and furnished spots with the mobilities of galacturonic and 4-O-methylglucuronic acids. Traces of glucuronic acid appeared only under conditions such that demethylation of the 4-O-methyl acid might have occurred. Hydrolysis of larger amounts furnished D-galacturonic acid, as yet syrupy, [α]+32° instead of +51°, and 4-O-methyl-D-glucuronic acid, [α]+20° instead of +35°. The latter, especially if present as non-reducing end-groups, would account for the strong precipitation of ketha gum in Type II antipneumococcal horse sera. When ketha gum was esterified, reduced and hydrolysed, the two acids disappeared almost entirely, a component corresponding to 4-O-methylglucose was observed, and the hexose content was increased. Oxidation of the gum with periodate, followed by reduction and hydrolysis, caused the disappearance of the 4-O-methylglucuronic acid and most of the galacturonic acid. Comparison of analyses and chromatograms of the original gum with those of samples recovered from the specific precipitates with Types I and II antisera showed little or no fractionation.
虽然据报道凯塔胶含有阿拉伯糖、半乳糖、木糖、一种未鉴定的中性糖和葡萄糖醛酸,但它与I型抗肺炎球菌马血清有明显的交叉反应,由此得出结论,D - 半乳糖醛酸必定是其另外一种成分。I型肺炎球菌的荚膜多糖是免疫特异性的决定因素,其由超过50%的D - 半乳糖醛酸组成。凯塔胶水解产物的色谱分析证实了阿拉伯糖、半乳糖和木糖的存在,并显示出具有半乳糖醛酸和4 - O - 甲基葡萄糖醛酸迁移率的斑点。仅在可能发生4 - O - 甲基酸脱甲基化的条件下才出现痕量的葡萄糖醛酸。大量水解得到的是仍呈糖浆状的D - 半乳糖醛酸,其旋光度为[α]+32°而非 +51°,以及4 - O - 甲基 - D - 葡萄糖醛酸,旋光度为[α]+20°而非 +35°。尤其是当后者以非还原端基形式存在时,这可以解释凯塔胶在II型抗肺炎球菌马血清中强烈沉淀的现象。当凯塔胶被酯化、还原和水解时,这两种酸几乎完全消失,观察到一种对应于4 - O - 甲基葡萄糖的成分,并且己糖含量增加。用过碘酸盐氧化该胶,随后进行还原和水解,导致4 - O - 甲基葡萄糖醛酸和大部分半乳糖醛酸消失。将原始胶的分析结果和色谱图与从I型和II型抗血清的特异性沉淀物中回收的样品的分析结果和色谱图进行比较,结果显示几乎没有分馏现象或者根本没有分馏现象。