Isolation and Structure of a New Ganglioside Molecular Species

Abstract

A ganglioside molecular species [LLG‐3 (1)] has been obtained from the water‐soluble lipid fraction of the CHCl3/MeOH extract of the starfish Linckialaevigata. On the basis of chemical and spectroscopic findings, the structure of 1 has been elucidated. Negative‐ion FABMS provided important information concerning both the structure of the sugar moiety and the molecular mass of the ganglioside. On the other hand, positive‐ion FABMS/MS of [M + Na]+ ions obtained in the positive‐ion FABMS of the ceramide lactoside (4) derived from 1 indicated the structure of the fatty acid chain of the ceramide moiety. 1 represents a new ganglioside molecular species possessing a 2→11‐linked tandem‐type disialosyl moiety.

Structure-Activity Relationship Study of the Neuritogenic Potential of the Glycan of Starfish Ganglioside LLG-3 ‡

“…Recently, we reported the first total synthesis of ganglioside LLG-3, which was originally identified in the starfish Linckia laevigata [ 36 , 56 ], and showed that synthetic LLG-3 could stimulate neuritogenesis in rat PC12 cells [ 40 ]. In this report, we investigated the neuritogenic potential of the glycan moiety of LLG-3.…”

Total Synthesis of the Echinodermatous Ganglioside LLG-3 Possessing the Biological Function of Promoting the Neurite Outgrowth

“…Ganglioside DSG-A (9- O -Me-NeuAcα­(2,6)­Glcβ­(1,1)-ceramide) and LLG-3 (8- O -Me-NeuAcα­(2,11)­NeuGcα­(2,3)-Galβ­(1,4)­Glcβ­(1,1)­ceramide, 1 ), which are bioactive metabolites found in the sea urchin Diadema setosum and the starfish Linckia laevigata , , respectively, promote excellent neuritogenesis of a rat pheochromocytoma cell line (PC-12 cells) in the presence of nerve growth factor (NGF). Furthermore, the activity of neurite outgrowth of DSG-A (40.8%) and LLG-3 (63.1%) was greater than that of GM1 (25.4% and 47.0%, respectively).…”

A Chemoenzymatic Total Synthesis of the Neurogenic Starfish Ganglioside LLG‐3 Using an Engineered and Evolved Synthase

“…Echinodermatous gangliosides are also characterized by highly heterogeneous sphingolipids, with structures uncommon in vertebrate systems predominating. Several gangliosides from starfish, including the tetrasaccharide LLG-3 from Linckia laevigata (1, Scheme 1), [4] show promising evidence of neuritogenic activity in cell culture and are thus of pharmacological interest. [5] LLG-3 from natural sources exists as a heterogeneous mixture of ceramides with variability in both the d-ribophytosphingosine and a-hydroxy acid components.…”