Structure of a New Neuritogenic‐Active Ganglioside from the Sea Cucumber <i>Stichopus japonicus</i>

Kaneko, Masakatsu; Kisa, Fumiaki; Yamada, Koji; Miyamoto, Tomofumi; Higuchi, Ryota

doi:10.1002/ejoc.200390141

Cited by 43 publications

(31 citation statements)

References 16 publications

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“…[2][3][4][5][6][7][8][9][10][11] In the study of the GSLs of the sea cucumber Holothuria pervicax, we reported the isolation and structure of ten glucocerebrosides revealing a very close resemblance in structure.9) However, all these compounds still exist as a mixture of regio-isomers for terminal methyl groups in the side chain of the long-chain base (LCB) moiety, namely a mixture of iso and ante-iso isomers as shown in Fig. 1.…”

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Constituents of Holothuroidea, 15. Isolation of Ante-iso Type Regio-isomer on Long Chain Base Moiety of Glucocerebroside from the Sea Cucumber Holothuria leucospilota

Yamada

Wada

Onaka

et al. 2005

CHEMICAL & PHARMACEUTICAL BULLETIN

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In our continuing research on biologically active glycosphingolipids (GSLs) from echinoderms, a series of studies on the isolation and structural elucidation of the GSLs from sea cucumber species have been performed in our laboratory. [2][3][4][5][6][7][8][9][10][11] In the study of the GSLs of the sea cucumber Holothuria pervicax, we reported the isolation and structure of ten glucocerebrosides revealing a very close resemblance in structure.9) However, all these compounds still exist as a mixture of regio-isomers for terminal methyl groups in the side chain of the long-chain base (LCB) moiety, namely a mixture of iso and ante-iso isomers as shown in Fig. 1. Continuing the previous studies, the separation of the mixture of the regio-isomers was conducted. In this paper, we report on the isolation of an ante-iso type regio-isomer of glucocerebroside from its parent glucocerebroside molecular species HLC-2, an abundant compound obtained from the whole bodies of the sea cucumber Holothuria leucospilota (Nisekuronamako in Japanese). 12)The less polar lipid fraction, which was obtained from the chloroform/methanol extract of the whole bodies of H. leucospilota, was subjected to repeated silica gel column chromatography to give three cerebroside molecular species, HLC-1, HLC-2, and HLC-3, each showing a single spot on silica gel thin-layer chromatography (TLC).In the IR and positive-ion FAB mass spectra of HLC-1, HLC-2, and HLC-3, strong hydroxy and amide absorptions and a series of molecular ion peaks are observed. Their 13 C-NMR spectra (Fig. 1, Table 1) exhibit the characteristic signals of a sphingosine-type b-glucocerebroside possessing an unsubstituted fatty acid (HLC-1), a sphingosine-type b-glucocerebroside possessing a 2-hydroxy fatty acid (HLC-2), and a phytosphingosine-type b-glucocerebroside possessing a 2-hydroxy fatty acid (HLC-3), respectively. Therefore, they are suggested to be the molecular species of three typical types of glucocerebrosides. Their structures shown in Fig. 1 were characterized by comparison of their 13 C-NMR spectral data with those of known glucocerebrosides 2-4) hitherto obtained, and by means of the results of their chemical degradations, namely methanolysis followed by the GC-MS analysis of the methanolysis products, fatty acid methyl ester (FAM), and LCB, as shown in Fig. 2 and Experimental. The geometry (Z) of the double bond in the unsaturated fatty acyl moiety of HLC-1-HLC-3 was determined from the d value (27.4, 27.5) of the allylic carbon atoms obtained from their 1 H-detected heteronuclear multiple-bond connectivity (HMBC) spectra (Fig. 3) ; 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan: and b Department of Medical Electronics Engineering, Faculty of Engineering, Towa University; 1-1-1 Chikusigaoka, Minamiku, Fukuoka 815-0036, Japan. Received February 14, 2005; accepted March 22, 2005 An ante-iso type regio-isomer on the long chain base moiety of a glucocerebroside, HLC-2-A, has been isolated from its parent glucocerebroside molecular species HLC-2 composed of ...

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Constituents of Holothuroidea, 15. Isolation of Ante-iso Type Regio-isomer on Long Chain Base Moiety of Glucocerebroside from the Sea Cucumber Holothuria leucospilota

Yamada

Wada

Onaka

et al. 2005

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…After Biological Assay Neuritogenic activity of 1 in PC12 cells was observed according to the method previously reported. 16) …”

Section: Gc-ms Analysis Of Fam From 1 a Fam Mixture From 1 Was Subjecmentioning

confidence: 99%

Isolation and Structure of a GD3-Type Ganglioside Molecular Species Possessing Neuritogenic Activity from the Starfish Luidia maculata

et al. 2004

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In the course of our continuing research on biologically active glycosphingolipids (GSLs) from echinoderms, a series of studies on the isolation and structure elucidation of GSLs from starfish have been performed in our laboratory. [1][2][3][4][5][6] In the study of the GSLs of the starfish Luidia maculata (yatsudesunahitode in Japanese), we reported on the isolation, structure and biological activities of cerebrosides, 7) ceramide lactosides, 8) sulfatide, 9) and gangliosides. 10,11) Continuing the previous studies, further isolation and characterization of the more polar ganglioside from L. maculata were conducted. In this paper, we report on the isolation and structure of a ganglioside molecular species from the whole bodies of L. maculata. The biological activity of the ganglioside is also reported.The polar lipid fraction, which was obtained from the chloroform/methanol extract of the whole bodies of L. maculata, was subjected to repeated column chromatography to give a polar compound, designated LMG-4 (1), showing a single spot on silica gel thin-layer chromatography (TLC).Compound 1 shows strong hydroxy and amide absorptions in the IR spectrum and has a positive reaction against resorcinol reagent.12) The negative FAB-MS exhibits a series of quasimolecular ion peaks [MϪH] Ϫ at m/z: 1500-1620. Therefore 1 is suggested to be a molecular species of ganglioside.The structure of the ceramide moiety was examined first. When 1 was methanolyzed with methanolic hydrochloric acid, a mixture of fatty acid methyl esters (FAM) and longchain bases (LCBs) was obtained. The FAM mixture was analyzed by GC-MS, which revealed the presence of three components. These were characterized as methyl 2-hydroxydocosanoate (major), methyl 2-hydroxytricosanoate, and methyl 2-hydroxytetracosanoate. The LCB mixture was found to be composed of such phytosphingosines as 2-amino-1,3,4-trihydroxy-heptadecane (major), 2-amino-1,3,4-trihydroxy-octadecane, and 2-amino-1,3,4-trihydroxy-nonadecane, based on GC-MS analysis of its TMS derivative (Chart 1).The structure of the sugar moiety of 1 was established as follows. The GC analysis of hexitol acetate derivatives of the neutral sugars, which were obtained by hydrolysis, reduction,

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“…[2][3][4][5][6][7][8][9][10][11][12][13][14] In the study of the GSLs of the sea cucumber Cucumaria echinata (gumi in Japanese), we reported the isolation and structure of glucocerebrosides 2,4) and monosialogangliosides.…”

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Constituents of Holothuroidea, 18. Isolation and Structure of Biologically Active Disialo- and Trisialo-Gangliosides from the Sea Cucumber Cucumaria echinata

et al. 2006

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In the course of our continuing research on biologically active glycosphingolipids (GSLs) from echinoderms, a series of studies on the isolation and structural elucidation of the GSLs from sea cucumber species have been performed in our laboratory. [2][3][4][5][6][7][8][9][10][11][12][13][14] In the study of the GSLs of the sea cucumber Cucumaria echinata (gumi in Japanese), we reported the isolation and structure of glucocerebrosides 2,4) and monosialogangliosides.1) In a continuation of the preceding studies, 1) the further isolation and characterization of the more polar biologically active gangliosides from the sea cucumber C. echinata were carried out to develop novel medicinal resources from natural marine products. In this paper, we report the isolation and characterization of three new disialoand trisialo-gangliosides from the whole bodies of C. echinata. The biological activities of the gangliosides are also reported. The polar lipid fraction, which was obtained from the chloroform/methanol extract of the whole bodies of C. echinata, was subjected to repeated silica gel column chromatography to yield four compounds (6-9), each showing a single spot on TLC.In its 13 C-NMR spectrum (Fig. 1, Table 1), compound 6 exhibits the characteristic signals of a sphingosine-type ceramide, with a nonhydroxylated fatty acid and a sugar moiety at C-1 [d: 70.6 (C-1), 54.1 (C-2), 72.5 (C-3), 131.0 (C-4), 132.3 (C-5), and 175.9 (C-1Ј)]. The 13 C-NMR spectrum of 6 also features signals due to four anomeric carbons at d 104.8, 101.2, 101.0, and 100.5, two of which (d 101.2, 101.0) are quaternary carbon signals, indicating the presence of two sialic acid residues. Therefore 6 is suggested to be a sphingosine-type ganglioside, with nonhydroxylated fatty acid groups and four monosaccharide units. Furthermore, 6 is presumed to have normal-type fatty acids and ante-iso-type long-chain bases (LCBs), since the carbon signals for the terminal methyl groups are observed at d 14.1 (normal form) and d 11.5 and 19.2 (ante-iso form) in the 13 C-NMR spectrum (Fig. 1, Table 1).The structure of the ceramide moiety was examined first. When 6 was methanolyzed with methanolic hydrochloric acid, a mixture of fatty acid methyl esters (FAMs) and an LCB was obtained, together with methyl glucoside and fucoside. The FAM mixture was analyzed using GC-MS, which revealed the presence of 10 components (see Experimental), and the major one was characterized as methyl docosanoate. The LCB was found to be 2-amino-1,3-dihydroxy-4-heptadecene based on GC-MS analysis of its TMS derivative. The stereochemistry of the ceramide moiety of 6 is presumed to be (2S,3R,4E) the same as that of the precursor compound, glucocerebroside CE-1, 4) coexisting in the same organism. The structure of the tetrasaccharide moiety of 6 was established as follows. The presence of glucose (Glc) and fucose (Fuc) was obvious from the results of the methanolysis of 6 (vide supra). A detailed analysis of the 13 C-NMR spectrum of 6 revealed the characteristic signals [d 172.3 and 172.4...

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Structure of a New Neuritogenic‐Active Ganglioside from the Sea Cucumber Stichopus japonicus

Cited by 43 publications

References 16 publications

Constituents of Holothuroidea, 15. Isolation of Ante-iso Type Regio-isomer on Long Chain Base Moiety of Glucocerebroside from the Sea Cucumber Holothuria leucospilota

Constituents of Holothuroidea, 15. Isolation of Ante-iso Type Regio-isomer on Long Chain Base Moiety of Glucocerebroside from the Sea Cucumber Holothuria leucospilota

Isolation and Structure of a GD3-Type Ganglioside Molecular Species Possessing Neuritogenic Activity from the Starfish Luidia maculata

Constituents of Holothuroidea, 18. Isolation and Structure of Biologically Active Disialo- and Trisialo-Gangliosides from the Sea Cucumber Cucumaria echinata

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