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Constituintes QuÃmicos dos ZoantÃdeos Palythoa caribaeorum (Duchassaing & Michelotti, 1860) e Protopalythoa Variabilis (Duerden, 1898) / Chemical Constituents of the zoanthids Palythoa caribaeorum (Duchassaing & Michelotti, 1860) and Protopalythoa variabilis (Duerden, 1898)Josà Gustavo Lima de Almeida 24 November 2011 (has links)
nÃo hà / Este trabalho descreve a composiÃÃo quÃmica das espÃcies marinha Palythoa caribaeorum e Protopalythoa variabilis, coletadas no municÃpio de Paracuru-CE. O fracionamento cromatogrÃfico do extrato hexÃnico de P. caribaeorum, resultou no isolamento de quatro esterÃides tetracÃclico de esqueleto ergostano: 24(R)-ergost-5-en-3-ol (P-1); 5,8-epidioxi-24(R)-ergost-6-en-3-ol (P-2); 24(R)-ergost-5-en-3,7-diol (P-4) e 24(R)-7-hidroperoxi-ergost-5-en-3-ol (P-7), um derivado do glicerol, 1-O-hexadecilglicerol (P-3) e quatro ceramidas: N-(2S,3R,4E,8E,1,3-dihidroxi-4,8-octadecadieno)hexadecanamida (P-5); N-(2S,3R,4E,1,3-dihidroxi-4-octadeceno)-hexadecanamida (P-6), N-[2S,3R,4E,8E,1-(2â-metilamino-etanosulfonila)-3-hidroxi-4,8-octadecaÂdieno]hexadecanamida (P-8) e N-[2S,3R,4E,1-(2â-metilaminoetano-sulfonila)-3-hidroxi-4-octadeceno]hexadecanamida (P-9). Do fracionamento cromatogrÃfico do extrato etanÃlico, foi possÃvel isolar o esterÃide 24(R)-ergost-7-en-3,56-triol (P-10) e o nucleosÃdeo 2-metil-timidina (P-11). Do estudo quÃmico do extrato hexÃnico de P. variabilis obteve-se os mesmos constituintes quÃmicos isolados de P. caribaeorum (P-1, P-2, P-3 e P-4) e as quatro ceramidas (P-5, P-6, P-8 e P-9). AlÃm destes compostos foi isolado um Ãster de cadeia alifÃtica, hexadecanoato de nonila (P-12) e o esterÃide Ãcido 24(R)-B-norergostan-3-5-diol-6-carboxÃlico (P-13). O potencial citotÃxico e antifÃngico das ceramidas foi avaliado, entretanto, estas nÃo apresentaram atividade. Os compostos foram isolados atravÃs de cromatografia de adsorÃÃo em gel de sÃlica e cromatografia lÃquida de alta eficiÃncia. As estruturas dos compostos obtidos foram elucidadas utilizando tÃcnicas espectroscÃpicas e espectromÃtricas, tais como: espectrometria de massa acoplada a cromatografia gasosa (CG/EM); espectrometria de massa de alta resoluÃÃo (EMAR); espectroscopia na regiÃo do infravermelho (IV) e RessonÃncia MagnÃtica Nuclear (RMN 1H, 13C e 15N) atravÃs de sequÃncias de pulsos uni e bidimensionais e comparaÃÃo com dados de RMN na literatura. / This work describes the chemical composition of the marine species Palythoa
caribaeorum and Protopalythoa variabilis, both collected at Paracuru beach, state of
CearÃ. The cromatographic fractionation of the hexane extract from P. caribaeorum
resulted in the isolation of four tetracyclic sterols possessing the ergostan skeleton:
24(R)-ergost-5-en-3b-ol (P-1); 5 a,8a-epidioxy-24(R)-ergost-6-en-3b-ol (P-2); 24(R)-
ergost-5-en-3b,7a-diol (P-4) and 24(R)-7a-hydroperoxy-ergost-5-en-3b-ol (P-7), a
glycerol derivative, 1-O-hexadecylglycerol (P-3) and four ceramides: N-
(2S,3R,4E,8E,1,3-dihydroxy-4,8-octadecadienyl)hexadecanamide (P-5); N-
(2S,3R,4E,1,3-dihydroxy-4-octadecenyl)hexadecanamide (P-6); N-[2S,3R,4E,8E,1-(2â-
methylamino-ethanosulfonyl)-3-hydroxy-4,8-octadecaenyl]hexadecanamide (P-8) and
N-[2S,3R,4E,1-(2â-methylaminoethano-sulfonyl)-3-hydroxy-4-octadecenyl]hexadecanamide
(P-9). The cromatographic fractionation of the ethanol extract permited the
isolation of a steroid, 24(R)-ergost-7-en-3b,5a,6b-triol (P-10) and a nucleoside 2-
methyltimidine (P-11). Column chromatography of the hexane extract of P. variabilis
led to the isolation of nonyl hexadecanoate (P-12), the sterol 24(R)-B-norergostan-3b-
5b-diol-6b-carboxylic acid (P-13) and the same chemical constituents previously
isolated from P. caribaeorum (P-1, P-2, P-3 e P-4) including the four ceramides (P-5,
P-6, P-8 e P-9). The citotoxic and antifungal properties of all ceramides were evaluated,
nevertheless none of them showed any activity. All compounds were isolated through
adsorption column cromatography over silica gel followed by high performance liquid
chromatography. The structures of the isolated compounds were elucidated using
spectrometric techniques, such as: GC/MS, HRESIMS, IR and NMR (1H, 13C and 15N)
through 1D and 2D pulse sequences and, whenever the case, comparison with literature
data
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