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温和酸水解海地瓜硫酸软骨素:结构、降解机制与抗凝活性。

Mild acid hydrolysis on Fucan sulfate from Stichopus herrmanni: Structures, depolymerization mechanism and anticoagulant activity.

机构信息

State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 650201, China; Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Wulumuqi 830000, China.

School of Pharmaceutical Sciences, South-Central University for Nationalities, Wuhan 430074, China; State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 650201, China.

出版信息

Food Chem. 2022 Nov 30;395:133559. doi: 10.1016/j.foodchem.2022.133559. Epub 2022 Jun 22.

DOI:10.1016/j.foodchem.2022.133559
PMID:35777210
Abstract

Fucan sulfate (FS) from sea cucumbers possesses linear sequences with repeating units that differ principally in the pattern of sulfation and position of glycosidic linkage. FS from Stichopus herrmanni (ShFS) was preliminarily identified as the relatively simple structure {-3)-L-Fuc-(α1-}n. Herein, mild acid hydrolysis was employed on ShFS to yield 21 oligosaccharides. Analyses on their structures complemented the features of ShFS to refine its spectral signal assignments. Combining with the methylation analysis, unit L-Fuc was determined as the micro-component in its intact structure. The irregularity came from minor sulfation on O-4. Temperature and acid concentration were the critical parameters to the depolymerization and formation of oligosaccharides. Meanwhile, a three-step cleavage of the hydrolysis mechanism involving the partial O-2 de-sulfation and preferential cleavage between Fuc and Fuc was proposed. Bioactivity assays revealed that the Mw 15-16 kDa conferred the potent anticoagulation via inhibiting the thrombin activity mediated by heparin cofactor II.

摘要

海参硫酸多糖(FS)具有线性序列,其重复单元主要在硫酸化模式和糖苷键位置上有所不同。来自糙海参(ShFS)的 FS 被初步鉴定为相对简单的结构{-3)-L-岩藻糖-(α1-}n。在此,对 ShFS 进行了温和酸水解,得到了 21 种寡糖。对其结构的分析补充了 ShFS 的特征,从而完善了其光谱信号的归属。结合甲基化分析,确定单元 L-岩藻糖是其完整结构中的微量成分。不规则性来自 O-4 上的少量硫酸化。温度和酸浓度是解聚和寡糖形成的关键参数。同时,提出了水解机制的三步裂解,涉及部分 O-2 去硫酸化和岩藻糖与岩藻糖之间的优先裂解。生物活性测定表明,Mw 为 15-16 kDa 的物质通过抑制肝素辅因子 II 介导的凝血酶活性发挥强烈的抗凝作用。

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