RESUMO
Three novel bile acid derivatives, petromylidenes Aâ»C (1â»3), featuring uncommon alkylidene adductive scaffolds, were isolated from water conditioned with sexually mature male sea lampreys (Petromyzon marinus). Their structures were elucidated by mass spectrometry and NMR spectroscopy, and by comparison to spectral data of related structures. The identification of compounds 1â»3, further illustrates the structural diversity of the 5α bile salt family. Compounds 1â»3 exhibited notable biological properties as well, including high olfactory potencies in adult sea lampreys and strong behavioral attraction of ovulated female sea lampreys. Electro-olfactogram recordings indicated that the limit of detection for 1 was 10-9 M, 2 was 10-11 M, and 3 was less than 10-13 M. These results suggested 1â»3 were likely male pheromones, which guide reproductive behaviors in the sea lamprey.
Assuntos
Ácidos e Sais Biliares/farmacologia , Mucosa Olfatória/efeitos dos fármacos , Petromyzon , Atrativos Sexuais/farmacologia , Comportamento Sexual Animal/efeitos dos fármacos , Animais , Ácidos e Sais Biliares/química , Ácidos e Sais Biliares/isolamento & purificação , Feminino , Limite de Detecção , Espectroscopia de Ressonância Magnética , Masculino , Espectrometria de Massas , Estrutura Molecular , Atrativos Sexuais/química , Atrativos Sexuais/isolamento & purificaçãoRESUMO
Sea lamprey, Petromyzon marinus, rely heavily on chemical cues that mediate their life history events, such as migration and reproduction. Here, we describe petromyzone A-C (1-3), three novel bile alcohols that are highly oxidized and sulfated, isolated from water conditioned with spermiated male sea lamprey. Structures of these compounds were unequivocally established by spectroscopic analyses and by comparison with spectra of known compounds. Electro-olfactogram recordings showed that 1 at 10-11 M was stimulatory to the adult sea lamprey olfactory epithelium, while 2 and 3 were stimulatory at 10-13 M. Behavioral assays indicated that 1 is attractive, 2 is not attractive or repulsive, and 3 is repulsive to ovulated female sea lamprey. The results suggest that 1 and 2 may be putative pheromones that mediate chemical communication in sea lamprey. The identification of these three components enhances our understanding of the structures and functions of sex pheromone components in this species and may provide useful behavioral manipulation tools for the integrated management of sea lamprey, a destructive invader in the Laurentian Great Lakes.
Assuntos
Colestanóis/química , Colestanóis/metabolismo , Petromyzon/fisiologia , Atrativos Sexuais/química , Atrativos Sexuais/fisiologia , Animais , Cromatografia Líquida de Alta Pressão , Cromatografia em Camada Fina , Sinais (Psicologia) , Feminino , Masculino , Espectrometria de Massas , Estrutura Molecular , Mucosa Olfatória/fisiologia , Ovulação , Esteroides/química , Esteroides/metabolismoRESUMO
Two novel sulfated bile salt-like dienones, featuring either a unique, rearranged side chain or a rare cis-11,12-diol on the steroidal C-ring, herein named petromyzene A (1) and B (2), respectively, were isolated from water conditioned with spawning male sea lamprey (Petromyzon marinus; a jawless vertebrate animal). The structures of these natural products were elucidated by mass spectrometry and NMR spectroscopy. Petromyzenes A and B exhibited high olfactory potency for adult sea lamprey and strong behavioral attraction for spawning females.