Constituents of Holothuroidea, 17. Isolation and Structure of Biologically Active Monosialo-Gangliosides from the Sea Cucumber Cucumaria echinata

Kisa, Fumiaki; Yamada, Koji; Miyamoto, Tomofumi; Inagaki, Michio; Higuchi, Ryota

doi:10.1248/cpb.54.982

Cited by 22 publications

(20 citation statements)

References 21 publications

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“…[1][2][3][4][5][6][7] Continuing the previous studies, three cerebroside molecular species (BAC-1, BAC-2 and BAC-3) was obtained from the less polar lipid fraction of CHCl 3 /MeOH extract of sea cucumber Bohadschia argus (Janomenamako in Japanese). The structures of BAC-1, BAC-2 and BAC-3 could be determined by hitherto reported chemical and spectroscopic methods 2,4,5) as the molecular species of typical types of glucocerebrosides, 2,4,5) namely, a sphingosine-type b-glucocerebroside possessing non-hydroxy fatty acid (BAC-1), a sphingosine-type b-glucocerebroside possessing 2-hydroxy fatty acid (BAC-2), and phytosphingosine-type b-glucocerebroside possessing 2-hydroxy fatty acid (BAC-3), respectively (data not shown), as revealed in Fig.…”

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Isolation and Structure of a Galactocerebroside from the Sea Cucumber Bohadschia argus

Ikeda

Inagaki

Yamada

et al. 2009

CHEMICAL & PHARMACEUTICAL BULLETIN

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Isolation and Structure of a Galactocerebroside from the Sea Cucumber Bohadschia argus

Ikeda

Inagaki

Yamada

et al. 2009

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…1 H-and 13 C-NMR spectra were recorded on a Jeol GX-270 spectrometer (270, 67.8 MHz) or a Varian Unity-500 spectrometer (500, 125 MHz). Negative-ion FAB-MS spectra were acquired with a Jeol JMS-SX-102 mass spectrometer (xenon atom beam; matrix, triethanolamine).…”

Section: Methodsmentioning

confidence: 99%

“…[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.…”

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confidence: 90%

“…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.…”

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confidence: 99%

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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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“…We attempted to determine the absolute configuration (D or L) of the sialic acid residues in the gangliosides 3,4) from the sea cucumber Cucumaria echinata.…”

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Determination of the Absolute Configuration of Sialic Acids in Gangliosides from the Sea Cucumber Cucumaria echinata

Kisa

Yamada

Miyamoto

et al. 2007

CHEMICAL & PHARMACEUTICAL BULLETIN

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Gangliosides, an important group of glycosphingolipids due to their biological functions, 1) are characterized by the presence of one or more moles of sialic acid, N-acetylneuraminic acid (NeuAc) or N-glycolylneuraminic acid (NeuGc), in their carbohydrate parts. In general, naturally occurring sialic acids have been believed to be the D-form on the basis of biosynthetic evidence, i.e., NeuAc is synthesized from pyruvic acid and N-acetyl-D-mannosamine enzymatically. 2)However, there has been no report on the determination of the absolute configuration of the sialic acid residues in gangliosides. We attempted to determine the absolute configuration (D or L) of the sialic acid residues in the gangliosides 3,4) from the sea cucumber Cucumaria echinata.For the determination of the absolute configuration of aldoses in gangliosides, we have used the Hara method.5) However, this method cannot be applied to sialic acids directly. Therefore we prepared aldose from sialic acid, preserving the absolute configuration of the parent sialic acid, and then applied the Hara method to the aldose. As shown in Fig. 1, D(L)-arabinose should be obtained from D(L)-sialic acid in the process. First, this assumption was proved.D-NeuAc (1) was acetylated to give pentaacetate (2), which was methanolyzed with HCl-MeOH to yield methyl 2-O-methylneuraminate (3). Protection of the diol in the side chain of 3 with acetone afforded an isopropyridene derivative (4). Oxidation of 4 with NaIO 4 gave a dial derivative (5). Finally, compound 5 was hydrolyzed to separate arabinose (6). The absolute configuration of 6 was verified as being the Dform using the Hara method. On the other hand, L-NeuAc (7), which was synthesized from L-glucose using the authentic method, 6) gave L-arabinose in the same manner as 1. Thus the fact that D(L)-sialic acid could be converted to D(L)-arabinose was confirmed, as shown in Fig. 1.Next, this method was applied to the gangliosides SJG-1, CG-1, CEG-3, CEG-4, CEG-5, CEG-6, HLG-3, CEG-8, and CEG-9 3,4) from the sea cucumber C. echinata. The nine gangliosides were each methanolyzed and the sialic acid derivatives (3) produced were converted to ketals (4). Periodic acid oxidation of 4 followed by acidic hydrolysis of the oxidation products 5 gave arabinoses (6). Compound 6, obtained from each ganglioside, was determined to be the D-form using the Hara method, as shown in Fig. 2. Accordingly, the sialic acid residues (NeuAc and NeuGc) in the gangliosides from C. echinata must be the D-form. To the best of our knowledge, this is the first report of the determination of the absolute configuration of the sialic acid Determination of the Absolute Configuration of Sialic Acids inGangliosides from the Sea Cucumber Cucumaria echinata Fumiaki KISA, Koji YAMADA, Tomofumi MIYAMOTO, Masanori INAGAKI, and Ryuichi HIGUCHI* Faculty of Pharmaceutical Sciences, Kyushu University; 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan. Received March 15, 2007; accepted April 6, 2007 Enantiomeric pairs of sialic acid, D-and L-NeuAc (N-...

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Constituents of Holothuroidea, 17. Isolation and Structure of Biologically Active Monosialo-Gangliosides from the Sea Cucumber Cucumaria echinata

Cited by 22 publications

References 21 publications

Isolation and Structure of a Galactocerebroside from the Sea Cucumber Bohadschia argus

Isolation and Structure of a Galactocerebroside from the Sea Cucumber Bohadschia argus

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

Determination of the Absolute Configuration of Sialic Acids in Gangliosides from the Sea Cucumber Cucumaria echinata

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