硫酸角质素衍生二糖的光谱表征

Spectroscopic characterisation of disaccharides derived from keratan sulfates.

作者信息

Huckerby T N, Brown G M, Dickenson J M, Nieduszynski I A

机构信息

Polymer Centre, School of Physics and Materials, Lancaster University, England.

出版信息

Eur J Biochem. 1995 Apr 1;229(1):119-31. doi: 10.1111/j.1432-1033.1995.tb20446.x.

DOI:10.1111/j.1432-1033.1995.tb20446.x

PMID:7744022

Abstract

Skeletal keratan sulfates have been degraded by three independent techniques and the resultant, borohydride-reduced, disaccharides have been characterised by NMR spectroscopy. The 1H and 13C (where available) chemical shifts are reported for the following substances, where GalNAc-ol represents N-acetyl-galactosaminitol, GlcNAc-ol represents N-acetyl-glucosaminitol, GlcNAc(6S)-ol represents N-acetyl-glucosaminitol 6-O-sulfate and 2,5AnMan(6S)-ol represents 2,5-anhydro-D-mannitol 6-O-sulfate. (a) GlcNAc(6S)beta(1-3)Gal-ol, isolated after keratanase (from Pseudomonas sp.) digestion. (b) Gal beta(1-4)GlcNAc(6S)-ol and Gal(6S)beta(1-4) GlcNAc(6S)-ol, the 1H chemical shifts have been reported previously [Brown, G. M., Huckerby, T. N., Morris, H. G., Abram, B. L. & Nieduszynski, I. A. (1994) Biochemistry 33, 4836-4846; Brown, G. M., Huckerby, T. N. & Nieduszynski, I. A. (1994) Eur. J. Biochem. 224, 281-308], GlcNAc(6S)beta(1-6)GalNAc-ol, [formula: see text], [formula: see text], all isolated after keratanase II digestion. (c) Gal beta(1-4)2,5AnMan(6S)-ol and Gal(6S)beta(1-4)2,5AnMan(6S)-ol, isolated after hydrazinolysis and nitrous acid digestion. In addition, the model compounds Gal beta(1-4)GlcNAc-ol and Gal beta(1-6)GlcNAc-ol have also been examined by 1H and 13C NMR spectroscopy. The value of these data for microstructural analysis of keratan sulfate samples is discussed.

摘要

硫酸角质素已通过三种独立技术进行降解，所得经硼氢化钠还原的二糖已通过核磁共振光谱进行表征。以下物质的¹H和¹³C（如适用）化学位移已被报道，其中GalNAc - ol代表N - 乙酰 - 半乳糖胺醇，GlcNAc - ol代表N - 乙酰 - 葡糖胺醇，GlcNAc(6S) - ol代表N - 乙酰 - 葡糖胺醇6 - O - 硫酸盐，2,5AnMan(6S) - ol代表2,5 - 脱水 - D - 甘露糖醇6 - O - 硫酸盐。(a) GlcNAc(6S)β(1 - 3)Gal - ol，在角质酶（来自假单胞菌属）消化后分离得到。(b) Galβ(1 - 4)GlcNAc(6S) - ol和Gal(6S)β(1 - 4)GlcNAc(6S) - ol，¹H化学位移先前已有报道[布朗，G.M.，哈克比，T.N.，莫里斯，H.G.，阿布拉姆，B.L. & 尼杜申斯基，I.A.（1994年）生物化学33，4836 - 4846；布朗，G.M.，哈克比，T.N. & 尼杜申斯基，I.A.（1994年）欧洲生物化学杂志224，281 - 308]，GlcNAc(6S)β(1 - 6)GalNAc - ol，[化学式：见原文]，[化学式：见原文]，均在角质酶II消化后分离得到。(c) Galβ(1 - 4)2,5AnMan(6S) - ol和Gal(6S)β(1 - 4)2,5AnMan(6S) - ol，在肼解和亚硝酸消化后分离得到。此外，模型化合物Galβ(1 - 4)GlcNAc - ol和Galβ(1 - 6)GlcNAc - ol也已通过¹H和¹³C核磁共振光谱进行检测。讨论了这些数据在硫酸角质素样品微观结构分析中的价值。