Journal of Natural Prorlcrrts Vol. 56, No. 12,pp. 2104-2113, December 1993
2104
SPONGE FATTY ACIDS, 5 .l CHARACTERIZATION OF COMPLETE SERIES OF 2-HYDROXY LONG-CHAIN FATTY ACIDS IN PHOSPHOLIPIDS OF TWO SENEGALESE MARINE SPONGES FROM THE FAMILY SUBERITIDAE: PSEUDOSUBERITES SP. AND SUBERITES MASSA G u s BARNATHAN, JEAN-MCHEL KORNPROBST,*
Institut des Sciences et Organism de la Mer (ISOMer),Group SMAB, I , rue Gaston Veil, 44035 Nantes Cedex 01, France PIERREDOUMENQ, Centre de Spectroscopie Molkulain, Faculte'des Sciences et Techniques de Saint JtWme, Universitid'Aix-MarseilleIll, 13397 Marseille Cedex 13, France JOSEPHMIUS,
Ecole Nomwle Suphieure, Nouakchott, Mauritanie, and NICOLE BOURY-ESNALJLT Cmtre GOchnologie de Marseille, Station Marine d'Endoum, 13007 Marseille, France
ABsmm.-Phospholipid fatty acid composition was studied in two Senegalese sponges of the family Suberitidae.More than fifty acids were identified in either P s d s d w i t e c sp. or Suberites mssa. A series of 2-hydroxy long-chain fatty acids (C22to C2,)accounted for almost 50% of the total acid mixture of Pseudosrtberittv sp., including 2-hydroxyhexacosanoic acid (26%) and the unusual 2-hydroxy-heptacosanoic acid not yet reported in any sponge. A series of 3-hydroxy shon-chain fatty acids was also detected in this sponge. Two new fatty acids were identified in these sponges, namely 4,8-dimethyldecanoic and 12-methyl-(Z)-6-tridecenoic,in addition to the rare 13-methyl-(Z)-4-tetradecenoic.Su. mssa contained mainly 5,9dienoic and trienoic demospongic acids. For the first time, 2-hydroxy long-chain fatty acid methyl esters were analyzed by gc-Ft-ir, and the corresponding N-acyl pyrrolidide derivatives by gc-ms.
As part of our ongoing comparative studies of fatty acids and sterols of sponges from Senegalese coastal waters (1-4), we investigated two sponges belonging to the family Suberitidae (Order Hadromerida): Pseudosubetites sp. Topsent (Hadromerida)and Suberites massa Nardo (Hadromerida). To our knowledge, no phospholipid fatty acids from any sponges of the family Suberitidae have yet been described. Among the numerous phospholipid fatty acid compositions reported to date, the Occurrence of 2-oxo-substituted fatty acids in sponge phospholipids has been described only a few times. The Senegalesesponge Higginsia tethyoides (Axinellida, Axinellidae) was rhe first shown to contain several unusual 2-methoxy fatty acids (up to 28 carbon atoms) (5,6).A series of 2-acetoxy fatty acids (up to 30 carbon atoms) was then encountered in Polymastia gleneni (Hadromerida, Polymastidae), ( 7 ) .However it was only in 1989 that Carballeira and Lopez (8) identified 2-hydroxy fatty acids for the first time in phospholipids from Amphimedon cmpressa (Haposclerida, Niphatidae) and then from Aplysina archer; and Verongda gigantea (Verongida, Aplysinidae) (9). Two other marine sponges, Tethya T p t a and Spheciospongia cuspidifercl (Hadromerida, Tethyidae and Spirastrellidae, respectively), were shown to contain 2-hydroxy long-chain fatty acids (9,lO). Recently, an interesting finding was the Occurrence of six novel is0 and anteiso branched 2-hydroxy fatty acids in a Caribbean sponge, Smenospongia aurea (Dictyoceratida, Thorectidae) (11). In this paper, we report the occurrence of a complete series of 2-hydroxy long-chain 'For Part 4 of this series, see Barnathan et a!. (4).
December 19937 Barnathan et a/.: 2-Hydroxy Long-chain Fatty Acids
2 105
fatty acids, including the longest one ever identified in sponge phospholipids, namely 2-hydroxyheptacosanoicacid. In addition, we describe the first use ofgc-Ft-ir for analysis of 2-hydroxy long chain fatty acid methyl esters and of gc-ms for the corresponding pyrrolidides. W e also report here the identification of two new short-chain fatty acids, namely 4,8-dimethyldecanoic and 12-methyl-(Z)-6-tridecenoic. RESULTS AND DISCUSSION Tlc analysis showed that the main phospholipids from Pseudosuberztes sp. and Su. mssa are phosphatidylethanolamine and phosphatidylserine. As indicated in Table 1, more than 50 fatty acids were identified in each sponge, most being present in both organisms. TABLE1. Phospholipid Fatty Acids from Two Senegalese Marine Sponges of the Familv Suberitidae.' Source
ECL (OV-1)
Fatty acids
Fatty acids 4,8-Dimethyldecan~ic~ .......... 12-Methyl-6-tridecenoicb 12-Methyltridecanoic . . . . . . . . . . .
4,8,12-Trimethyltridecanoic. . . . . . 12-Methyltetradecanoic
.........
14-Methylhexadecanoic . . . . . . . . . Heptadecanoic . . . . . . . . . . . . . . . . 9,12-Octadecadienoic 11-Octadecenoic . . . . . . . . . . . . . . .
16-Methyloctadecanoic . . . . . . . . . . 11-Nonadecenoic 12-Nonadecenoic Icosanoic . . . . . . . . . . . . . . . . . . . . . 19-Methylicosanoic 18-Methylicosanoic. . . . . . . . . . . . . Tricosanoic . . . . . . . . . . . . . . . . . . . 2 1-Methyltricosanoic 17-Tetracosenoic . Tetracosanoic . . . . . . . . . . . . . . . . . 22-Methyltetracosanoic 16-Pentacosenoic . . . . . . . . . . . . . . Pentacosanoic . . . . . . . . . . . . . . . . . 17-Hexacosenoic
4,8-DM-10:0 i-6-14: 1 i-14:0 14:O i-4- 15:1 4,8,12-TM-13:0 i-15:0 ai-1 5:O 15:O i-16:0 8-16:l 9-16:l 16:O 7-Me-6-161 i-17:O ai- 17:O 17:O 9,12-18:2 i-18:O 9-18:l 11-18:l 18:O ai-19:O 11-19:l 12-1911 19:O i-20:0 20:o i-21:0 ai-2 1:O 23:O ai-24:O 17-24:l 24:O ai-2 5 :O 16-25:l 25:O 17-26:l
10.92* 13.40 13.60 14.00 14.40d 14.47 14.63 14.73 15.00 15.63 15.74 15.80 16.00 16.34 16.65 16.72 17.00 17.52 17.66 17.76 17.84 18.00 18.73 18.82 18.85 19.00 19.64 20.00 20.63 20.72 23.00 23.74 23.80 24.00 24.72 24.72 25.00 25.69
Suberites mssa (% ) 0.5 tr. 0.6 1.8 0.5
0.5 0.5 1.6
-
6.5 0.4
-
1.o 0.5 1.3 1.7 1.6 3.6
-
0.5
-
0.5 0.6 0.6 0.8 0.5 0.5 1.o 0.6 0.9 1.1 0.5
0.4 1.8 3.1 0.6 11.8 3.0 0.7 2.5 3.0
-
2.6 5.1 1.o 0.7 1.1 1.0 0.5 tr. 1.4 2.8 6.2 0.3
-
1.o 1.o 0.8 0.5 0.4 0.6 tr.
-
tr. 0.2 0.5 -
-
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Journal of Natural Products
Wol. 56, No. 1 2
TABLE 1. Continued. ECL
Fatty acids
Suberites massa (%)
(OV-1) 18-2611 19-26:l 26:O
25.78 25.75 26.00
-
5.5
2.6 1.1
tr.
2-OH-140 2-OH-1 5:O 2-OH-i-1610 2-OH-16:O 2-OH- 17:O 2-OH- 18:O 2-OH-22:O 2-OH-23 10 2-OH-240 2-OH-2530 2-OH-26:O 2-OH-27:O
15.14 16.13 16.88 17.10 18.14 19.12 23.15 24.22 25.26 26.28 27.28 28.26
0.3 0.6 0.5 0.6 0.5 0.5 0.9 9.7 9.2 25.9 2.7
0.4 tr. 0.4 0.5 0.2 0.2 0.4 0.5 -
13.38 15.35 16.32 17.32 19.36
0.6 0.3 0.4 0.2 0.2
-
3-Hydroxyoctadecanoic . . . . . . . . . .
3-OH-12:O 3-OH-140 3-OH-1 5:O 3-OH- 16:O 3-0H-18:O
-
A5'9-Demospongicacids 5,9-Pentacosadienoic . . . . . . . . . . . 5,9-Hexacosadienoic . . . . . . 5,9-Heptacosadienoic . . . . . 25-Methyl-5,9-heptacosadienoic. . . 5,9,19-Octacosatrienoic . . . . . . . . . 5,9,21-Octacosatrienoic . . . . . . . . . 5,9-Octacosadienoic . . . . . . . . . . . .
5,9-25:2 5,9,-26:2 5,9-27:2 ai-5,9-28:2 5,9,19-28:3 5,542 1-283 5,9-28:2
24.50 25.52 26.50 27.32 27.39 27.40 27.52
0.5 7.8 0.6 1.6 0.4 1.6
0.9 21.3 3.3 11.1 0.7 -
18-Hexacosenoic . . . . . . . . . . . . . . . 19-Hexacosenoic . . . . . . . . . . . . . . . Hexacosanoic . . . . . . . . . . ... 2-Hydroxy fatty acids 2-Hydroxytetradecanoic . . . . . . . . . 2-Hydroxypentadecanoic . . . . . . . . 2-Hydroxy-14-methylpentadecanoic 2-Hydroxyhexadecanoic . . . . . . . . . 2-Hydroxyheptadecanoic . . . . . . . . 2-Hydroxyoctacosanoic . . . . . . . . . . 2-Hydroxydocosanoic . . . . . . . . . . . 2-Hydroxytricosanoic . . . . . . . 2-Hydroxytetracosanoic . . . . . . . . . 2-Hydroxypentacosanoic . . . . . . . . . 2-Hydroxyhexacosanoic . . . . . . . . . 2-Hydroxyheptacosanoic' . . . . . . . . 3-Hydroxy fatty acids 3-Hydroxydcdecanoic . . . . . . . . . . . 3-Hydroxytetradecanoic . . . . 3-Hydroxypentadecanoic . . . . . . . . 3-Hydroxyhexadecanoic . . . . . . . . .
'ECL=equivalent chain length. i=iso; ai=anteiso. Ideni 22:O; 22:O; 27:O; 28:O. %Jot previously found in nature. 'First reported in sponge phospholipids.
d minor fatty acids (%
