Chen Si-Cong, Qin Xianjin, Xiong Nanyu, Lin Lisha, Wu Yanfen, Li Qin, Sun Dongyue, Xiong De-Cai, Callmann Cassandra E, Wu Mingyi, Ye Xin-Shan
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, and Chemical Biology Center, Peking University, Beijing, China.
State Key Laboratory of Natural Medicines, School of Traditional Chinese Pharmacy, China Pharmaceutical University, Nanjing, China.
Nat Commun. 2025 May 10;16(1):4364. doi: 10.1038/s41467-025-59632-2.
Fucoidan, a sulfated glycan derived from brown algae, has garnered significant attention for its anticoagulant properties. However, the structural complexity and heterogeneity of naturally extracted fucoidan have hindered a comprehensive understanding of its structure-activity relationship, limiting the development of fucoidan-based anticoagulant drugs. To address this challenge, we synthesize a diverse library of 58 distinct fucoidans with multiple contiguous 1,2-cis glycosidic bonds, ranging from disaccharides to dodecasaccharides, using a highly efficient preactivation-based one-pot glycosylation strategy. This library includes compounds with various sulfation patterns (2,3-O-di-, 3,4-O-di-, and 2,3,4-O-tri-sulfation) encompassing nearly all possible fucoidan structures. In vitro anticoagulant assays demonstrate that both molecular size and degree of sulfation play crucial roles in anticoagulant potency. Notably, compounds 29, 30, 37, and 58 significantly prolong human plasma activated partial thromboplastin time (APTT), comparable to the effect of enoxaparin, without affecting prothrombin time (PT) or thrombin time (TT). This selective inhibition of the intrinsic coagulation pathway suggests a reduced risk of bleeding, highlighting the therapeutic potential of these fucoidans as safer anticoagulant agents.
岩藻依聚糖是一种从褐藻中提取的硫酸化聚糖,因其抗凝血特性而备受关注。然而,天然提取的岩藻依聚糖结构复杂且具有异质性,这阻碍了对其构效关系的全面理解,限制了基于岩藻依聚糖的抗凝血药物的开发。为应对这一挑战,我们采用高效的基于预活化的一锅法糖基化策略,合成了一个包含58种不同岩藻依聚糖的文库,这些岩藻依聚糖具有多个连续的1,2-顺式糖苷键,从二糖到十二糖不等。该文库包括具有各种硫酸化模式(2,3-O-二硫酸化、3,4-O-二硫酸化和2,3,4-O-三硫酸化)的化合物,涵盖了几乎所有可能的岩藻依聚糖结构。体外抗凝血试验表明,分子大小和硫酸化程度在抗凝血效力中都起着关键作用。值得注意的是,化合物29、30、37和58显著延长了人血浆活化部分凝血活酶时间(APTT),与依诺肝素的效果相当,且不影响凝血酶原时间(PT)或凝血酶时间(TT)。这种对内源性凝血途径的选择性抑制表明出血风险降低,突出了这些岩藻依聚糖作为更安全抗凝血剂的治疗潜力。