Marine natural products

This review covers the literature published in 2003 for marine natural products, with 619 citations (413 for the period January to December 2003) referring to compounds isolated from marine microorganisms and phytoplankton, green algae, brown algae, red algae, sponges, coelenterates, bryozoans, molluscs, tunicates and echinoderms. The emphasis is on new compounds (656 for 2003), together with their relevant biological activities, source organisms and country or origin. Biosynthetic studies or syntheses that lead to the revision of structures or stereochemistries have been included (78), including any first total syntheses of a marine natural product.     

Marine natural products

This review covers the literature published in 2002 for marine natural products, with 579 citations (413 for the period January to December 2002) referring to compounds isolated from marine microorganisms and phytoplankton, green algae, brown algae, red algae, sponges, coelenterates, bryozoans, molluscs, tunicates and echinoderms. The emphasis is on new compounds (677 for 2002), together with their relevant biological activities, source organisms and country of origin. Syntheses that lead to the revision of structures or stereochemistries have been included (114), including any first total syntheses of a marine natural product.     

Marine natural products

This review covers the literature published in 2004 for marine natural products, with 693 citations (491 for the period January to December 2004) referring to compounds isolated from marine microorganisms and phytoplankton, green algae, brown algae, red algae, sponges, coelenterates, bryozoans, molluscs, tunicates and echinoderms. The emphasis is on new compounds (716 for 2004), together with their relevant biological activities, source organisms and country of origin. Biosynthetic studies (8), and syntheses (80), including those that lead to the revision of structures or stereochemistries, have been included.     

Marine natural products

This review covers the literature published in 2005 for marine natural products, with 704 citations (493 for the period January to December 2005) referring to compounds isolated from marine microorganisms and phytoplankton, green algae, brown algae, red algae, sponges, coelenterates, bryozoans, molluscs, tunicates and echinoderms. The emphasis is on new compounds (812 for 2005), together with their relevant biological activities, source organisms and country of origin. Biosynthetic studies, first syntheses, and syntheses that lead to the revision of structures or stereochemistries, have been included.     

Marine natural products

This review covers the literature published in 2006 for marine natural products, with 758 citations (534 for the period January to December 2006) referring to compounds isolated from marine microorganisms and phytoplankton, green algae, brown algae, red algae, sponges, cnidaria, bryozoans, molluscs, tunicates and echinoderms. The emphasis is on new compounds (779 for 2006), together with their relevant biological activities, source organisms and country of origin. Biosynthetic studies, first syntheses, and syntheses that lead to the revision of structures or stereochemistries, have been included.     

A new compound, jolynamine, from marine brown alga Jolyna laminarioides

A new compound, jolynamine (1), was isolated from the marine brown alga Jolyna laminarioides collected from the coast of Karachi, Pakistan. In addition, four known compounds, namely saringosterol (2), loliolide (3), methyl-4-hydroxybenzoate (4) and propyl-4-hydroxybenzoate (5), were isolated for the first time from the marine brown alga Iyengaria stellata, and two known compounds, namely 3,4,5-trimethylaniline (6) and harmine (7), were isolated for the first time from the marine brown alga Melanothamnus afaqhusainii. Compound 6 is synthetically known but was isolated for the first time from a natural source. The structures of these compounds were elucidated with the help of powerful spectroscopic techniques. Furthermore, the methanolic extracts of both algae showed anti-microbial activities against various bacteria and fungi.     

Marine natural products

Covering: 2010. Previous review: Nat. Prod. Rep., 2011, 28, 196. This review covers the literature published in 2010 for marine natural products, with 895 citations (590 for the period January to December 2010) referring to compounds isolated from marine microorganisms and phytoplankton, green, brown and red algae, sponges, cnidarians, bryozoans, molluscs, tunicates, echinoderms, mangroves and other intertidal plants and microorganisms. The emphasis is on new compounds (1003 for 2010), together with the relevant biological activities, source organisms and country of origin. Biosynthetic studies, first syntheses, and syntheses that lead to the revision of structures or stereochemistries, have been included.     

Marine natural products

This review covers the marine natural products literature for the year 2000 and is organized phylogenetically, with sections on marine microorganisms and phytoplankton, green algae, brown algae, red algae, sponges, coelenterates, bryozoans, molluscs, tunicates. echinoderms and miscellaneous marine organisms. There is an emphasis on new structures, stressing their biological activities, source organisms and countries of origin, and also syntheses that confirm the structures of known compounds. The review contains 869 structures and 592 references, of which 434 appeared between January and December 2000.     

八十年代海洋天然有机化学的进展

八十年代以来,海洋天然有机化学仍然继续发展,大量新的化合物,尤其是具有生理活性的化合物不断出现,海洋天然物的生物合成和人工合成研究也有新的进展。在海洋生物中,研究得最多的是海藻和海绵,其次便是珊瑚。     

Vanadium bromoperoxidase-catalyzed biosynthesis of halogenated marine natural products

Marine red algae (Rhodophyta) are a rich source of bioactive halogenated natural products. The biogenesis of the cyclic halogenated terpene marine natural products, in particular, has attracted sustained interest in part because terpenes are the biogenic precursors of many bioactive metabolites. The first enzymatic asymmetric bromination and cyclization of a terpene, producing marine natural products isolated from red algae, is reported. Vanadium bromoperoxidase (V-BrPO) isolated from marine red algae (species of Laurencia, Plocamium, Corallina) catalyzes the bromination of the sesquiterpene (E)-(+)-nerolidol producing alpha-, beta-, and gamma-snyderol and (+)-3beta-bromo-8-epicaparrapi oxide. alpha-Snyderol, beta-snyderol, and (+)-3beta-bromo-8-epicaparrapi oxide have been isolated from Laurencia obtusa, and each have also been isolated from other species of marine red algae. gamma-Snyderol is a proposed intermediate in other bicyclo natural products. Single diastereomers of beta-snyderol, gamma-snyderol, and mixed diastereomers of (+)-3beta-bromo-8-epicaparrapi oxide (de = 20-25%) are produced in the enzyme reaction, whereas two diastereomers of these compounds are formed in the synthesis with 2,4,4,6-tetrabromocyclohexa-2,5-dienone (TBCO). V-BrPO likely functions by catalyzing the two-electron oxidation of bromide ion by hydrogen peroxide producing a bromonium ion or equivalent in the active site that brominates one face of the terminal olefin of nerolidol. These results establish V-BrPO's role in the biosynthesis of brominated cyclic sesquiterpene structures from marine red algae for the first time.     

Determination of 11 low-molecular-weight carbonyl compounds in marine algae by high-performance liquid chromatography

A new analytical method is reported for the determination of 11 volatile carbonyl compounds isolated at room temperature from the headspace of marine algae. This method is based on the conversion of the carbonyl compounds to their 2,4-dinitrophenylhydrazone derivatives followed by high-performance liquid chromatography analysis. Using this method, 11 carbonyl compounds are detected and identified from the dynamic headspace sampling of 10 species of marine algae. Eight compounds are quantitated and the three remaining are only identified. Under optimized conditions, all carbonyl compounds are separated in 32 min. The detection and quantitation limits of the high-performance liquid chromatography method are, respectively, in the range of 0.26-0.85 ng/g of algae (formaldehyde) to 13.77-45.90 ng/g of algae (E)-2-hexenal. The calibration curves are linear in the concentration range of 2.0-1000 microg/L of solution, corresponding to 0.34-170.00 ng/g of algae. Acetaldehyde and propanal are the most abundant carbonyl compounds identified, with concentrations as high as 980 and 790 ng/g, respectively. The present work, as far as we know, is the first analytical methodology that has been developed to determine low-molecular-weight carbonyl compounds in marine algae. Because many species of marine algae are used as human food, the reported method should be useful to investigators studying the nutritional value as well as oxidative spoilage of fresh and preserved marine algae that is destined for human consumption.     

Ecological leads for natural product discovery: novel sesquiterpene hydroquinones from the red macroalga Peyssonnelia sp.

Pharmacologically-motivated marine natural product investigations have yielded a large variety of structurally unique compounds with interesting biomedical properties, but the natural roles of these molecules often remain unknown. While secondary metabolites may function as antimicrobial chemical defenses, few studies have examined this hypothesis. In the present investigation, chromatographic fractions from 69 collections of Fijian red macroalgae representing at least 43 species were evaluated for growth inhibition of three microbial pathogens and saprophytes of marine macrophytes. At least one microbe was suppressed by fraction(s) of all evaluated algae, suggesting that antimicrobial defenses are common among tropical seaweeds. From these leads, peyssonoic acids A-B (1-2), novel sesquiterpene hydroquinones, were isolated from the crustose red alga Peyssonnelia sp. At ecologically realistic concentrations, both compounds inhibited growth of Pseudoalteromonas bacteriolytica, a bacterial pathogen of marine algae, and Lindra thalassiae, a fungal pathogen of marine algae, and exhibited modest antineoplastic activity against ovarian cancer cells. The peyssonoic acids included one novel carbon skeleton and illustrated the utility of ecological studies in natural product discovery.     

Bioactive Metabolites from Marine Algae as Potent Pharmacophores against Oxidative Stress-Associated Human Diseases: A Comprehensive Review

In addition to cancer and diabetes, inflammatory and ROS-related diseases represent one of the major health problems worldwide. Currently, several synthetic drugs are used to reduce oxidative stress; nevertheless, these approaches often have side effects. Therefore, to overcome these issues, the search for alternative therapies has gained importance in recent times. Natural bioactive compounds have represented, and they still do, an important source of drugs with high therapeutic efficacy. In the “synthetic” era, terrestrial and aquatic photosynthetic organisms have been shown to be an essential source of natural compounds, some of which might play a leading role in pharmaceutical drug development. Marine organisms constitute nearly half of the worldwide biodiversity. In the marine environment, algae, seaweeds, and seagrasses are the first reported sources of marine natural products for discovering novel pharmacophores. The algal bioactive compounds are a potential source of novel antioxidant and anticancer (through modulation of the cell cycle, metastasis, and apoptosis) compounds. Secondary metabolites in marine Algae, such as phenolic acids, flavonoids, and tannins, could have great therapeutic implications against several diseases. In this context, this review focuses on the diversity of functional compounds extracted from algae and their potential beneficial effects in fighting cancer, diabetes, and inflammatory diseases.     

非水反相高效液相色谱法测定海藻中3种叶黄素类化合物

建立了非水反相高效液相色谱测定不同种类海藻中3种叶黄素类化合物的方法。采用超声波辅助提取海藻中的叶黄素类化合物,选用Alltima C18色谱柱分离,以甲醇-乙腈-丙酮为流动相系统,梯度洗脱分离,检测波长445 nm。结果表明,在选定的色谱条件下,待分析的3种叶黄素类化合物与其他化合物分离良好,在一定浓度范围内线性关系良好(紫黄素:6.24～624μg/L,环氧玉米黄素:4.56～456μg/L,玉米黄素:5.60～560μg/L)。该方法适用于不同海洋藻类中3种叶黄素类化合物的定量分析。     

Vanadium haloperoxidase-catalyzed bromination and cyclization of terpenes

Marine red algae (Rhodophyta) are a rich source of bioactive halogenated natural products, including cyclic terpenes. The biogenesis of certain cyclic halogenated marine natural products is thought to involve marine haloperoxidase enzymes. Evidence is presented that vanadium bromoperoxidase (V-BrPO) isolated and cloned from marine red algae that produce halogenated compounds (e.g., Plocamium cartilagineum, Laurencia pacifica, Corallina officinalis) can catalyze the bromination and cyclization of terpenes and terpene analogues. The V-BrPO-catalyzed reaction with the monoterpene nerol in the presence of bromide ion and hydrogen peroxide produces a monobromo eight-membered cyclic ether similar to laurencin, a brominated C15 acetogenin, from Laurencia glandulifera, along with noncyclic bromohydrin, epoxide, and dibromoproducts; however, reaction of aqueous bromine with nerol produced only noncyclic bromohydrin, epoxide, and dibromoproducts. The V-BrPO-catalyzed reaction with geraniol in the presence of bromide ion and hydrogen peroxide produces two singly brominated six-membered cyclic products, analogous to the ring structures of alpha and beta snyderols, brominated sesquiterpenes from Laurencia, spp., along with noncyclic bromohydrin, epoxide, and dibromoproducts; again, reaction of geraniol with aqueous bromine produces only noncyclic bromohydrin, epoxide, and dibromoproducts. Thus, V-BrPO can direct the electrophilic bromination and cyclization of terpenes.     

Discovery of New Cytotoxic Aplaminone Derivatives from the Sea Hare Aplysia kurodai and Elucidation of Their Accumulation from Local Sea Algae through the Food Chain

The shell-less herbivorous marine mollusk (sea hare) Aplysia kurodai is known to contain a variety of bioactive substances. While these compounds have been thought to originate from sea algae or their associated microbes, most of their origin and acquisition pathways are still unclear. Six new cytotoxic aplaminone derivatives, bromodopamine-terpenoid hybrid molecules, were isolated from A. kurodai. Among them, isoaplaminone had a reverse prenyl group at the C15 aliphatic chain, which is a rare structural feature from the viewpoint of terpenoid biosynthesis. Investigation for chemical components in A. kurodai and the sea algae collected at several different locations revealed that two major aplaminones were contained in the Laurencia complex species at specific sites. Our chemical and ecological studies provide new insights into the origin of marine alkaloid toxins and their dynamism through the food chain.     

Secondary Metabolites from Marine Sources with Potential Use as Leads for Anticancer Applications

The development of novel anticancer agents is essential to finding new ways to treat this disease, one of the deadliest diseases. Some marine organisms have proved to be important producers of chemically active compounds with valuable bioactive properties, including anticancer. Thus, the ocean has proved to be a huge source of bioactive compounds, making the discovery and study of these compounds a growing area. In the last few years, several compounds of marine origin, which include algae, corals, and sea urchins, have been isolated, studied, and demonstrated to possess anticancer properties. These compounds, mainly from securamines and sterols families, have been tested for cytotoxic/antiproliferative activity in different cell lines. Bioactive compounds isolated from marine organisms in the past 5 years that have shown anticancer activity, emphasizing the ones that showed the highest cytotoxic activity, such as securamines H and I, cholest-3β,5α,6β-triol, (E)-24-methylcholest-22-ene-3β,5α,6β-triol, 24-methylenecholesta-3β,5α,6β-triol, and 24-methylcholesta-3β,5α,6β-triol, will be discussed in this review. These studies reveal the possibility of new compounds of marine origin being used as new therapeutic agents or as a source of inspiration to develop new therapeutic agents.     

Natural product growth inhibitors of Mycobacterium tuberculosis

This review covers natural products (secondary metabolites) with reported growth inhibitory activity towards Mycobacterium tuberculosis or related organisms. Such compounds have been isolated from a variety of sources including terrestrial and marine plants and animals, and microorganisms, with the express intent of identifying novel scaffolds for the development of new antituberculosis agents. The literature from January 2003 to December 2005 (inclusive) is reviewed and 146 references to 353 compounds are cited. The compounds are presented in order of chemical type, namely lipids/fatty acids and simple aromatics, phenolics and quinones, peptides, alkaloids, terpenes (monoterpenoids, diterpenes, sesquiterpenes and triterpenes), steroids and miscellaneous structures.     

Omaezallene from Red Alga Laurencia sp.: Structure Elucidation,Total Synthesis,and Antifouling Activity

Natural antifouling products have been the subject of considerable attention. We screened marine algae for antifouling activity and discovered omaezallenes, the new bromoallene‐containing natural products isolated from the red alga Laurencia sp. Described is the isolation, structure elucidation, and total syntheses of omaezallenes. The relative and absolute configurations of natural omaezallenes were unambiguously established through total synthesis. The antifouling activities and ecotoxicity of omaezallenes were also evaluated.     

Report on three aliphatic dimethylarsinoyl compounds as common minor constituents in marine samples. An investigation using high-performance liquid chromatography/inductively coupled plasma mass spectrometry and electrospray ionisation tandem mass spectrometry

Three water-soluble aliphatic arsenicals, dimethylarsinoyl acetate (DMAA), dimethylarsinoyl ethanol (DMAE), and dimethylarsinoyl propionate (DMAP), were identified in marine biological samples. Sample extracts in methanol/water (1 + 1) were analysed by cation-exchange high-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICPMS). Eluate fractions from the HPLC/ICPMS analyses containing the compounds in question were collected and subjected to analysis by electrospray ionisation tandem mass spectrometry (ESI-MS/MS), which provided supportive evidence for the structures of the three compounds. The concentrations of the three arsenicals were determined in 37 marine organisms comprising algae, crustaceans, bivalves, fish and mammals by HPLC/ICPMS. The three arsenicals DMAA, DMAE and DMAP, which occurred at microg kg(-1) concentrations, were detected in 25, 23 and 17 of the 37 samples analysed, respectively. The limits of detection were 2-3 microg kg(-1) dry mass. The data illustrate that the three compounds are common minor constituents in marine samples. This is the first report on DMAE and DMAP as naturally occurring species in marine samples. The presence of DMAA and DMAE supports a proposed biosynthesis of arsenobetaine (AB) from dimethylarsinoylribosides. Alternative proposals, which explain the presence of the compounds in marine samples, are addressed briefly in the paper.