RESUMEN
Metabolomics has recently proven its usefulness as complementary tool to traditional morphological and genetic analyses for the classification of marine invertebrates. Among the metabolite-rich cnidarian order Zoantharia, Parazoanthus is a polyphyletic genus whose systematics and phylogeny remain controversial. Within this genus, one of the most studied species, Parazoanthus axinellae is prominent in rocky shallow waters of the Mediterranean Sea and the NE Atlantic Ocean. Although different morphotypes can easily be distinguished, only one species is recognized to date. Here, a metabolomic profiling approach has been used to assess the chemical diversity of two main Mediterranean morphotypes, the "slender" and "stocky" forms of P. axinellae. Targeted profiling of their major secondary metabolites revealed a significant chemical divergence between the morphotypes. While zoanthoxanthin alkaloids and ecdysteroids are abundant in both morphs, the "slender" morphotype is characterized by the presence of additional and bioactive 3,5-disubstituted hydantoin derivatives named parazoanthines. The absence of these specific compounds in the "stocky" morphotype was confirmed by spatial and temporal monitoring over an annual cycle. Moreover, specimens of the "slender" morphotype are also the only ones found as epibionts of several sponge species, particularly Cymbaxinella damicornis thus suggesting a putative ecological link.
Asunto(s)
Antozoos/química , Antozoos/metabolismo , Metaboloma , Metabolómica , Animales , Antozoos/anatomía & histología , Antozoos/genética , Biodiversidad , Mezclas Complejas/química , Genes Mitocondriales , Geografía , Mar Mediterráneo , FenotipoRESUMEN
This review is devoted to the application of MS using soft ionization methods with a special emphasis on electrospray ionization, atmospheric pressure photoionization and matrix-assisted laser desorption/ionization MS and tandem MS (MS/MS) for the elucidation of the chemical structure of native and modified lignins. We describe and critically evaluate how these soft ionization methods have contributed to the present-day knowledge of the structure of lignins. Herein, we will introduce new nomenclature concerning the chemical state of lignins, namely, virgin released lignins (VRLs) and processed modified lignins (PML). VRLs are obtained by liberation of lignins through degradation of vegetable matter by either chemical hydrolysis and/or enzymatic hydrolysis. PMLs are produced by subjecting the VRL to a series of further chemical transformations and purifications that are likely to alter their original chemical structures. We are proposing that native lignin polymers, present in the lignocellulosic biomass, are not made of macromolecules linked to cellulose fibres as has been frequently reported. Instead, we propose that the lignins are composed of vast series of linear related oligomers, having different lengths that are covalently linked in a criss-cross pattern to cellulose and hemicellulose fibres forming the network of vegetal matter. Consequently, structural elucidation of VRLs, which presumably have not been purified and processed by any other type of additional chemical treatment and purification, may reflect the structure of the native lignin. In this review, we present an introduction to a MS/MS top-down concept of lignin sequencing and how this technique may be used to address the challenge of characterizing the structure of VRLs. Finally, we offer the case that although lignins have been reported to have very high or high molecular weights, they might not exist on the basis that such polymers have never been identified by the mild ionizing techniques used in modern MS.
Asunto(s)
Lignina/análisis , Lignina/química , Espectrometría de Masas en Tándem/métodos , Presión Atmosférica , Hidrólisis , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción/métodosRESUMEN
While marine organisms such as bivalves, seagrasses and macroalgae are commonly used as biomonitors for the environment pollution assessment, widely distributed sponges received little attention as potential helpful species for monitoring programmes. In this study, the trace element and radionuclide bioaccumulation and retention capacities of some marine sponges were estimated in a species-comparative study using radiotracers technique. Six Mediterranean species were exposed to background dissolved concentrations of (110m)Ag, (241)Am, (109)Cd, (60)Co, (134)Cs, (54)Mn, (75)Se and (65)Zn allowing the assessment of the uptake and depuration kinetics for selected elements. Globally, massive demosponges Agelas oroides, Chondrosia reniformis and Ircinia variabilis displayed higher concentration factor (CF) than the erectile ones (Acanthella acuta, Cymbaxinella damicornis, Cymbaxinella verrucosa) at the end of exposure, suggesting that the morphology is a key factor in the metal bioaccumulation efficiency. Considering this observation, two exceptions were noted: (1) A. acuta reached the highest CF for (110m)Ag and strongly retained the accumulated metal without significant Ag loss when placed in depuration conditions and (2) C. reniformis did not accumulate Se as much as A. oroides and I. variabilis. These results suggest that peculiar metal uptake properties in sponges could be driven by specific metabolites or contrasting biosilification processes between species, respectively. This study demonstrated that sponges could be considered as valuable candidate for biomonitoring metal contamination but also that there is a need to experimentally highlight metal-dependant characteristic among species.
Asunto(s)
Poríferos/metabolismo , Oligoelementos/farmacocinética , Animales , Cinética , Radioisótopos/farmacocinética , Contaminantes Químicos del Agua/farmacocinéticaRESUMEN
Sponge natural product biosynthesis: A highly sensitive in vivo protocol based on (14)C radiolabeled precursors and beta-imager autoradiography allowed the unraveling of the origin of the pyrrole 2-aminoimidazole-containing key biosynthetic intermediate oroidin. Proline and lysine are now proposed as the early precursors of the pyrrole and the 2-aminoimidazole moieties of oroidin respectively.
Asunto(s)
Alcaloides/metabolismo , Axinella/metabolismo , Pirroles/metabolismo , Animales , Imidazoles/metabolismo , Lisina/metabolismo , Redes y Vías Metabólicas , Prolina/metabolismoRESUMEN
The chemical composition of the Caribbean sponge Pandaros acanthifolium was reinvestigated and led to the isolation of 12 new steroidal glycosides, namely, pandarosides E-J (1-6) and their methyl esters (7-12). Their structures were determined on the basis of extensive spectroscopic analyses, including two-dimensional NMR and HRESIMS data. Like the previously isolated pandarosides A-D (13-16), the new compounds 1-12 share an unusual oxidized D-ring and a cis C/D ring junction. The absolute configurations of the aglycones were assigned by interpretation of CD spectra, whereas the absolute configurations of the monosaccharide units were determined by chiral GC analyses of the acid methanolysates. The majority of the metabolites showed in vitro activity against three or four parasitic protozoa. Particularly active were the compounds 3 (pandaroside G) and its methyl ester (9), which potently inhibited the growth of Trypanosoma brucei rhodesiense (IC(50) values 0.78 and 0.038 microM, respectively) and Leishmania donovani (IC(50)'s 1.3 and 0.051 microM, respectively).
Asunto(s)
Antiprotozoarios/aislamiento & purificación , Antiprotozoarios/farmacología , Poríferos/química , Saponinas/aislamiento & purificación , Saponinas/farmacología , Esteroides/aislamiento & purificación , Esteroides/farmacología , Animales , Antiprotozoarios/química , Leishmania donovani/efectos de los fármacos , Biología Marina , Resonancia Magnética Nuclear Biomolecular , Océanos y Mares , Plasmodium falciparum/efectos de los fármacos , Saponinas/química , Esteroides/química , Trypanosoma brucei rhodesiense/efectos de los fármacos , Trypanosoma cruzi/efectos de los fármacosRESUMEN
Five new hydantoin alkaloids, named parazoanthines A-E (1-5), were isolated as the major constituents of the Mediterranean sea anemone Parazoanthus axinellae. Their structural elucidation was achieved through NMR spectroscopic and mass spectrometric analyses. The absolute configuration of the chiral compounds 1 and 4 was determined by comparison between experimental and TDDFT-calculated CD spectra. The configuration of the trisubstituted double bond of 2, 3, and 5 was deduced from the (3)J(H6-C4) coupling constant value. This family of alkaloids represents the first example of natural 3,5-disubstituted hydantoins that do not exhibit a methyl at N-3. All compounds were tested for their natural toxicity (Microtox assay), and parazoanthine C (3) exhibited the highest natural toxicity.
Asunto(s)
Alcaloides/aislamiento & purificación , Hidantoínas/aislamiento & purificación , Anémonas de Mar/química , Alcaloides/química , Alcaloides/farmacología , Animales , Hidantoínas/química , Hidantoínas/farmacología , Mar Mediterráneo , Estructura Molecular , Resonancia Magnética Nuclear BiomolecularRESUMEN
The chemical composition of the Caribbean sponge Pandaros acanthifolium was investigated and led to the isolation of seven new steroidal glycosides namely pandarosides A-D (1, 3, 4 and 6) along with the three methyl esters of pandarosides A, C, and D (2, 5 and 7). Their structures were characterized as 3beta-[beta-glucopyranosyl-(1-->2)-beta-glucopyranosyloxyuronic acid]-16-hydroxy-5alpha,14beta-poriferast-16-ene-15,23-dione (1) and its methyl ester (2), 3beta-[beta-glucopyranosyloxyuronic acid]-16-hydroxy-5alpha,14beta-poriferast-16-ene-15,23-dione (3), 3beta-[beta-glucopyranosyl-(1-->2)-beta-glucopyranosyloxyuronic acid]-16-hydroxy-5alpha,14beta-cholest-16-ene-15,23-dione (4) and its methyl ester (5), 3beta-(beta-glucopyranosyloxyuronic acid)-16-hydroxy-5alpha,14beta-cholest-16-ene-15,23-dione (6) and its methyl ester (7) on the basis of detailed spectroscopic analyses, including 2D NMR and HRESIMS studies. Pandarosides A-D and their methyl esters (1-7) are all characterized by a rare 2-hydroxycyclopentenone D-ring with a 14beta configuration. The absolute configuration of the aglycon part of pandaroside A (1) was assigned by comparison between experimental and TDDFT calculated circular dichroism spectra on the more stable conformer.