What Are and Where Are the Bioactive Terpenoids Metabolites from Dictyotaceae (Phaeophyceae)
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Revista Brasileira de Farmacognosia Brazilian Journal of Pharmacognosy 21(2): 216-228, Mar./Apr. 2011 What are and where are the bioactive terpenoids metabolites from Dictyotaceae (Phaeophyceae) Joel Campos De Paula,*,1 Magui A. Vallim,2 Valéria Laneuville Teixeira2 Article 1Programa de Pós-graduação em Biodiversidade Neotropical, Instituto de Biociências, Universidade Federal do Estado do Rio de Janeiro, Brazil, 2Programa de Pós-graduação em Biologia Marinha, Instituto de Biologia, Received 3 Jan 2011 Universidade Federal Fluminense, Brazil. Accepted 18 Jan 2011 Available online 13 May 2011 Abstract: Dictyotaceae are a rich source of secondary metabolites, especially terpenes. These natural products have been studied for their bioactivity for human and for their ecological role in nature. The present work highlights de diversity of Keywords: the Dictyotaceae terpenes, emphasizing their bioactivities and the biogeography of Dictyotaceae their sources. The sesquiterpenes are found in Padina, Dictyopteris and Taonia. secondary metabolites Although Dictyopteris and Padina can be found in all oceans, Taonia has a more terpenes restricted distribution. Diterpenes of mixed origin have been reported in Lobophora, biogeography Taonia and Stypopodium. Stypopodium is a typically tropical and warm temperate bioactivities genus. Diterpenes with the spatane and seco-spatanes skeletons are known from Spatoglossum, Stoechospermum and Rugulopteryx. Spatoglossum is distributed over all the tropical marine world. Stoechospermum is known to occur in the Indian Ocean and Rugulopteryx is distributed mainly in Asia and on the Pacific Coast of Australia. The genus Dictyota contains diterpenes as the major metabolite and are present in all oceans, reaching even the cold temperate regions of northern and southern hemispheres. The terpenoids from Dictyotaceae exhibit bioactivities such ISSN 0102-695X doi: 10.1590/S0102-695X2011005000079 as inhibition of herbivores and antifungal, cytotoxic, antibiotic, anti-inflammatory, insecticidal and antiviral activities. Introduction substances that can counteract the presence and multiplication of infection by the biological pathogens Many marine organisms are able to produce has increased. In this context, studies of natural substances derived from secondary metabolism. These metabolites have been shown to be a good alternative, metabolites, also called natural products, are present with a diversity of sources, chemical structures and from bacteria and algae to echinoderms, mollusks, applicability. The oceans, which cover 70% of the tunicates and vertebrates, through the sponges and biosphere, are also the cradle of life on Earth. Due to corals (Blunt et al., 2010). the longer existence of life in the marine environment, The knowledge of metabolites has helped to it harbors the largest Phyletic diversity of the planet. characterize the algae at different hierarchical levels The brown algae (Phaeophyceae) are a class of (divisions, classes etc.) down to species (De Paula almost exclusively marine organisms that have been et al., 2007), and has importance for phytochemical, explored for the bioactivity potential of its metabolic phylogenetic and ecological studies (Teixeira et products, especially those of the representative family al., 1991). Moreover, these substances have a high Dictyotaceae. Although it is only the third in number biotechnological potential, as evidenced by their use of species within the class, this family is a rich and in the food and pharmaceutical industris that generates diverse source of natural products, which makes it billions of dollars (Smit, 2004). the most studied with the greatest number of known Technological advances in disease diagnosis, metabolites. Dictytotaceae is represented by species combined with democratization of access to this with apical growth from a single cell or a row of cells technology, are reflected in the increase in the number making up the margin. The macromorphology of these of people diagnosed with diseases caused by biological species includes flabeliform to ribbonlike plants. agents. In response to this scenario, the search for Micromorphologically, all have reproductive elements 216 What are and where are the bioactive terpenoids metabolites from Dictyotaceae (Phaeophyceae) Joel Campos De Paula et al. with only one plumose flagellum, while the other Halogenated sesquiterpenes (whose main Phaeophyceae possess a pair of flagella. The chemistry sources are the red algae) are reported in Padina of Dictyotaceae natural products include a rich antillarum (Parameswaran et al., 1994, 1996) production of terpenoids molecules of different origins and Dictyopteris divaricata (Ji et al., 2009), and and are therefore important in studies of metabolites of sesquiterpenes without halogens in Dictyopteris marine origin. divaricata (Song et al., 2005, 2006; Qiao et al., 2009; Two biogenic pathways have been described Wen et al., 2009), D. undulata (Song et al., 2004a) for the terpenoid formation, the mevalonate pathway and Taonia atomaria (De Rosa et al., 1994). For the and the mevalonate-independent pathway via latter two genera, 36 and six species are recognized, deoxyxylulose phosphate (Dewick, 2002). Terpenoids respectively, while for Padina 37 species are still are composed of five carbon subunits (an isoprenoid) valid. The sesquiterpenes in which a phloroglucinol disposed in a configuration called head and tail and are unit is added were reported in Dictyopteris undulata classified according to the number of isoprenoid units (Ochi et al., 1979a; 1979b; Cortés et al., 2001; Dave incorporated. In Dictyotaceae and in particular in this et al., 1984) and Dictyopteris divaricata (Song et al., paper, the most bioactive products have three or four 2004b). Alhough Dictyopteris and Padina can be found isoprenoid units, corresponding to the sesquiterpenes in all oceans with predominant occurrence in tropical and diterpenes, respectively. These two classes of areas, Taonia is more restricted to the North Atlantic terpenoids can have many different structures and Ocean, Caribbean, Mediterranean, South Australia variants, including the addition of halogen atoms (the and Pakistan (Figure 1). The sesquiterpenes of these most common being chlorine or bromine) or fragments genera are known to exhibit activity as an inhibitor of from other biogenic pathways. In this latter case, herbivores and antifungal, cytotoxic, antibiotic and they are called terpenes of mixed origin, an example ichthyotoxic activities. Table 1 illustrates some of the being the incorporation of a phloroglucinol unit into a products and their activities. diterpene. Meroditerpenes, i.e., polycyclic diterpenes of As a natural source, the terpenes are strongly mixed biogenesis characterized by a methyl hydroquinone influenced by population distributions. For example, nucleus linked to a diterpenic chain, have been reported in Freitas et al., (2007) and Vallim et al. (2007) found Lobophora papenfussii (Gerwick & Fenical, 1982), Taonia differences in the diterpene expression by Dictyota atomaria (Ishitsuka et al., 1990), Stypopodium zonale mertensii in different distant beaches and Ali & Pervez (Gerwick & Fenical, 1981), S. flabelliforme (Gerwick et (2003a, 2003b) and Ali et al. (2003; 2004) described al., 1979) and S. schimperii (Sampli et al., 2000). These highly oxidized diterpenes from a seco-dolastane and metabolites can be linear, similar to those found in Fucales related dolastane producing Canistrocarpus population (Ishitsuka et al., 1979; Kusumi et al., 1979; Amico et al., from the Karachi coast of the Arabian Sea. 1982a,b;, Banaigs et al. 1982; 1983), or have polycyclic The present work is a bried description skeletons similar to each other, which may reveal a of terpenoid diversity in Dictyotaceae and their phylogenetic similarity between Stypopodium and Taonia. bioactivity, algae source and distribution in the oceans. Meroditerpene compounds were reported in Stypopodium These results were presented at the II Workshop on flabelliforme (Areche et al., 2009). This is a typically New Bioactivies from Macroalgae. tropical and warm temperate genus (Figure 2) with six currently accepted species, including S. flabelliforme, Materials and Methods S. schimperii and S. zonale that have been studied chemically. The meroditerpenes of these genera are known The Dictyotaceae bioactivities were taken to exhibit cytotoxic, anti-inflammatory, insecticidal, and from the original papers and/or the annual review series antivira activities. Table 2 illustrates some of the activities Marine Natural Products, published by Natural Product of meroditerpenes. Reports and covering the literature from 1977 (Faulkner, Besides the above mentioned skeletal types, 1984) to 2009 (Blunt et al., 2011). Only bioactivities Dictyotaceae are the second richest source of cyclic for which the active substance was described were terpenes from marine algae, after the genus Laurencia selected. No information was used from studies limited (Rhodophyta). More than 300 diterpenoids have to extracts or enriched fractions. The scientific names been reported, distributed in six genera. Diterpenes of the Dictyotaceae and their geographical distribution of the spatane and seco-spatane types are known were based on information from the site algaebase from Spatoglossum (S. schmittii and S. howleii), (Guiry & Guiry, 2011). Stoechospermum polypodioides and Rugulopteryx. While the first two genera exhibit growth via a small Results group of apical cells,