硫酸角质素的13C核磁共振光谱——对通过角质酶II消化从牛关节软骨硫酸角质素的非还原链末端衍生的五种唾液酸化五糖的归属

13C-NMR spectroscopy of keratan sulphates--assignments for five sialylated pentasaccharides derived from the non-reducing chain termini of bovine articular cartilage keratan sulphate by keratanase II digestion.

作者信息

Huckerby T N, Brown G M, Nieduszynski I A

机构信息

The Polymer Centre, School of Physics and Chemistry, Lancaster University, Bailrigg, England.

出版信息

Eur J Biochem. 1998 Feb 1;251(3):991-7. doi: 10.1046/j.1432-1327.1998.2510991.x.

DOI:10.1046/j.1432-1327.1998.2510991.x

PMID:9490077

Abstract

Skeletal keratan sulphate has been fragmented using the enzyme keratanase II, and 13C chemical-shift data are reported for five reduced sialylated pentasaccharides that derived from the non-reducing chain terminal region. They have the structures: NeuAc(alpha2-6)Gal(beta1-4)GlcNAc6S(beta1-3)Gal(beta1-4)GlcNAc6 S-ol, NeuAc(alpha2-3)Gal(beta1-4)GlcNAc6S(beta1-3)Gal(beta1-4)GlcNAc6 S-ol, NeuAc(alpha2-6)Gal(beta1-4)GlcNAc6S(beta1-3)Gal6S(beta1-4)++ +GlcNAc6S-ol, NeuAc(alpha2-3)Gal(beta1-4)GlcNAc6S(beta1-3)Gal(6S)(beta1-4)Glc NAc6S-ol, and NeuAc(alpha2-3)Gal(6S)(beta1-4)GlcNAc6S(beta1-3)Gal(6S)(beta1-4)++ +GlcNAc6S-ol, where GlcNAc6S-ol represents N-acetyl-glucosaminitol 6-O-sulphate and NeuAc represents N-acetylneuraminic acid. The use of these 13C-NMR spectroscopy data for the recognition of specific chain-capping structures within native keratan sulphates is discussed. In addition, examination of the data derived from the NeuAc(alpha2-6) capping structures strongly suggests that sulphation three residues away from the neuraminic acid cap has a profound effect upon the conformation of the capping region.

摘要

使用角蛋白酶II将硫酸角质素进行片段化处理，并报告了源自非还原链末端区域的五种还原唾液酸化五糖的13C化学位移数据。它们具有以下结构：NeuAc（α2-6）Gal（β1-4）GlcNAc6S（β1-3）Gal（β1-4）GlcNAc6S-ol、NeuAc（α2-3）Gal（β1-4）GlcNAc6S（β1-3）Gal（β1-4）GlcNAc6S-ol、NeuAc（α2-6）Gal（β1-4）GlcNAc6S（β1-3）Gal6S（β1-4）GlcNAc6S-ol、NeuAc（α2-3）Gal（β1-4）GlcNAc6S（β1-3）Gal（6S）（β1-4）GlcNAc6S-ol以及NeuAc（α2-3）Gal（6S）（β1-4）GlcNAc6S（β1-3）Gal（6S）（β1-4）GlcNAc6S-ol，其中GlcNAc6S-ol代表N-乙酰葡糖胺醇6-O-硫酸盐，NeuAc代表N-乙酰神经氨酸。讨论了利用这些13C-NMR光谱数据识别天然硫酸角质素中特定链封端结构的情况。此外，对源自NeuAc（α2-6）封端结构的数据进行研究强烈表明，距离神经氨酸封端三个残基处的硫酸化对封端区域的构象有深远影响。