Marine Drugs

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523 KiB

Open AccessArticle

Dereplication and Chemotaxonomical Studies of Marine Algae of the Ochrophyta and Rhodophyta Phyla

by Robert Brkljača, Emrehan Semih Gӧker and Sylvia Urban

Mar. Drugs 2015, 13(5), 2714-2731; https://doi.org/10.3390/md13052714 - 30 Apr 2015

Cited by 12 | Viewed by 6991

Abstract

Dereplication and chemotaxonomic studies of six marine algae of the Ochrophyta and one of the Rhodophyta phyla resulted in the detection of 22 separate compounds. All 16 secondary metabolites, including four new compounds (16–19), could be rapidly dereplicated using [...] Read more.

Dereplication and chemotaxonomic studies of six marine algae of the Ochrophyta and one of the Rhodophyta phyla resulted in the detection of 22 separate compounds. All 16 secondary metabolites, including four new compounds (16–19), could be rapidly dereplicated using HPLC-NMR and HPLC-MS methodologies in conjunction with the MarinLit database. This study highlights the advantages of using NMR data (acquired via HPLC-NMR) for database searching and for the overall dereplication of natural products. Full article

(This article belongs to the Special Issue Marine Natural Products - Advances in Separation, Characterisation and Chemical Profiling Methodologies)

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1078 KiB

Open AccessArticle

New Prenylated Aeruginosin, Microphycin, Anabaenopeptin and Micropeptin Analogues from a Microcystis Bloom Material Collected in Kibbutz Kfar Blum, Israel

by Shira Elkobi-Peer and Shmuel Carmeli

Mar. Drugs 2015, 13(4), 2347-2375; https://doi.org/10.3390/md13042347 - 15 Apr 2015

Cited by 35 | Viewed by 7236

Abstract

Thirteen new and eighteen known natural products were isolated from a bloom material of an assembly of various Microcystis spp. collected in November, 2008, from a commercial fishpond near Kibbutz Kfar Blum, the Jordan Valley, Israel. The new natural products included the prenylated [...] Read more.

Thirteen new and eighteen known natural products were isolated from a bloom material of an assembly of various Microcystis spp. collected in November, 2008, from a commercial fishpond near Kibbutz Kfar Blum, the Jordan Valley, Israel. The new natural products included the prenylated aeruginosin KB676 (1), microphycin KB921 (2), anabaenopeptins KB906 (3) and KB899 (4) and micropeptins KB928 (5), KB956 (6), KB970A (7), KB970B (8), KB984 (9), KB970C (10), KB1048 (11), KB992 (12) and KB1046 (13). Their structures were elucidated primarily by interpretation of their 1D and 2D nuclear magnetic resonance spectra and high-resolution mass spectrometry. Marfey’s and chiral-phase high performance liquid chromatography methods were used to determine the absolute configurations of their chiral centers. Aeruginosin KB676 (1) contains the rare (2S,3aS,6S,7aS)-Choi and is the first prenylated aeruginosin derivative described in the literature. Compounds 1 and 5–11 inhibited trypsin with sub-μM IC₅₀s, while Compounds 11–13 inhibited chymotrypsin with sub-μM IC₅₀s. The structures and biological activities of the new natural products and our procedures of dereplication are described. Full article

(This article belongs to the Special Issue Marine Natural Products - Advances in Separation, Characterisation and Chemical Profiling Methodologies)

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926 KiB

Open AccessCommunication

Solvent Separating Secondary Metabolites Directly from Biosynthetic Tissue for Surface-Assisted Laser Desorption Ionisation Mass Spectrometry

by David Rudd, Kirsten Benkendorff and Nicolas H. Voelcker

Mar. Drugs 2015, 13(3), 1410-1431; https://doi.org/10.3390/md13031410 - 16 Mar 2015

Cited by 10 | Viewed by 6469

Abstract

Marine bioactive metabolites are often heterogeneously expressed in tissues both spatially and over time. Therefore, traditional solvent extraction methods benefit from an understanding of the in situ sites of biosynthesis and storage to deal with heterogeneity and maximize yield. Recently, surface-assisted mass spectrometry [...] Read more.

Marine bioactive metabolites are often heterogeneously expressed in tissues both spatially and over time. Therefore, traditional solvent extraction methods benefit from an understanding of the in situ sites of biosynthesis and storage to deal with heterogeneity and maximize yield. Recently, surface-assisted mass spectrometry (MS) methods namely nanostructure-assisted laser desorption ionisation (NALDI) and desorption ionisation on porous silicon (DIOS) surfaces have been developed to enable the direct detection of low molecular weight metabolites. Since direct tissue NALDI-MS or DIOS-MS produce complex spectra due to the wide variety of other metabolites and fragments present in the low mass range, we report here the use of “on surface” solvent separation directly from mollusc tissue onto nanostructured surfaces for MS analysis, as a mechanism for simplifying data annotation and detecting possible artefacts from compound delocalization during the preparative steps. Water, ethanol, chloroform and hexane selectively extracted a range of choline esters, brominated indoles and lipids from Dicathais orbita hypobranchial tissue imprints. These compounds could be quantified on the nanostructured surfaces by comparison to standard curves generated from the pure compounds. Surface-assisted MS could have broad utility for detecting a broad range of secondary metabolites in complex marine tissue samples. Full article

(This article belongs to the Special Issue Marine Natural Products - Advances in Separation, Characterisation and Chemical Profiling Methodologies)

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804 KiB

Open AccessArticle

Preparative Separation of Sulfur-Containing Diketopiperazines from Marine Fungus Cladosporium sp. Using High-Speed Counter-Current Chromatography in Stepwise Elution Mode

by Binbin Gu, Yanying Zhang, Lijian Ding, Shan He, Bin Wu, Junde Dong, Peng Zhu, Juanjuan Chen, Jinrong Zhang and Xiaojun Yan

Mar. Drugs 2015, 13(1), 354-365; https://doi.org/10.3390/md13010354 - 9 Jan 2015

Cited by 30 | Viewed by 7490

Abstract

High-speed counter-current chromatography (HSCCC) was successively applied to the separation of three sulfur-containing diketopiperazines (DKPs) (including two new compounds cladosporin A (1) and cladosporin B (3), and a known compound haematocin (2)) from a marine fungus Cladosporium [...] Read more.

High-speed counter-current chromatography (HSCCC) was successively applied to the separation of three sulfur-containing diketopiperazines (DKPs) (including two new compounds cladosporin A (1) and cladosporin B (3), and a known compound haematocin (2)) from a marine fungus Cladosporium sp. The two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water at (1:1:1:1, v/v) and (2:1:2:1, v/v), in stepwise elution mode, was used for HSCCC. The preparative HSCCC separation was performed on 300 mg of crude sample yielding 26.7 mg of compound 3 at a purity of over 95%, 53.6 mg of a mixture of compounds 1 and 2, which was further separated by preparative-HPLC yielding 14.3 mg of compound 1 and 25.4 mg of compound 2 each at a purity of over 95%. Their structures were established by spectroscopic methods. The sulfur-containing DKPs suppressed the proliferation of hepatocellular carcinoma cell line HepG2. The present work represents the first application of HSCCC in the efficient preparation of marine fungal natural products. Full article

(This article belongs to the Special Issue Marine Natural Products - Advances in Separation, Characterisation and Chemical Profiling Methodologies)

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693 KiB

Open AccessArticle

Total Synthesis of Gobiusxanthin Stereoisomers and Their Application to Determination of Absolute Configurations of Natural Products: Revision of Reported Absolute Configuration of Epigobiusxanthin

by Yumiko Yamano, Kotaro Ematsu, Hiromasa Kurimoto, Takashi Maoka and Akimori Wada

Mar. Drugs 2015, 13(1), 159-172; https://doi.org/10.3390/md13010159 - 30 Dec 2014

Cited by 1 | Viewed by 6292

Abstract

(3R)-Gobiusxanthin stereoisomers (1a–d) were synthesized by stereoselective Wittig reaction of the (3R)-C₁₅-acetylenic tri-n-butylphosphonium salt 7 with C₂₅-apocarotenal stereoisomers 5a,b and 14a,b bearing four kinds of [...] Read more.

(3R)-Gobiusxanthin stereoisomers (1a–d) were synthesized by stereoselective Wittig reaction of the (3R)-C₁₅-acetylenic tri-n-butylphosphonium salt 7 with C₂₅-apocarotenal stereoisomers 5a,b and 14a,b bearing four kinds of 3,6-dihydroxy-ε-end groups. The validity of the reported stereochemistry of gobiusxanthin was demonstrated by the fact that the reported spectral data of natural gobiusxanthin were in agreement with those of synthetic (3R,3'S,6'R)-gobiusxanthin (1a). On the other hand, the reported CD spectral data of natural epigobiusxanthin, which has been assigned as (3R,3'R,6'R)-isomer (3'-epigobiusxanthin), were identical with those of synthetic (3R,3'S,6'S)-isomer 1d (6'-epigobiusxanthin) rather than those of the corresponding synthetic 3'-epi-isomer 1b. It was found that the stereochemistry at C3-position has little effect on the shape of their CD spectra. Thus, in order to reinforce the validity of the absolute configurations at C3-position of natural specimens, (3S,3'S,6'R)- and (3S,3'S,6'S)-stereoisomers 1e and 1f were also synthesized and a HPLC analytical method for four stereoisomers was established by using a column carrying a chiral stationary phase. The HPLC analysis has proven that the stereochemistry of the natural epigobiusxanthin is 3R,3'S,6'S. Full article

(This article belongs to the Special Issue Marine Natural Products - Advances in Separation, Characterisation and Chemical Profiling Methodologies)

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962 KiB

Open AccessArticle

Chemical Profiling (HPLC-NMR & HPLC-MS), Isolation, and Identification of Bioactive Meroditerpenoids from the Southern Australian Marine Brown Alga Sargassum paradoxum

by Robert Brkljača and Sylvia Urban

Mar. Drugs 2015, 13(1), 102-127; https://doi.org/10.3390/md13010102 - 29 Dec 2014

Cited by 25 | Viewed by 9550

Abstract

A phytochemical investigation of a southern Australian marine brown alga, Sargassum paradoxum, resulted in the isolation and identification of four new (5, 9, 10, and 15) and nine previously reported (1, 2, 6– [...] Read more.

A phytochemical investigation of a southern Australian marine brown alga, Sargassum paradoxum, resulted in the isolation and identification of four new (5, 9, 10, and 15) and nine previously reported (1, 2, 6–8, and 11–14) bioactive meroditerpenoids. HPLC-NMR and HPLC-MS were central to the identification of a new unstable compound, sargahydroquinal (9), and pivotal in the deconvolution of eight (1, 2, 5–7, and 10–12) other meroditerpenoids. In particular, the complete characterization and identification of the two main constituents (1 and 2) in the crude dichloromethane extract was achieved using stop-flow HPLC-NMR and HPLC-MS. This study resulted in the first acquisition of gHMBCAD NMR spectra in the stop-flow HPLC-NMR mode for a system solely equipped with a 60 μL HPLC-NMR flow cell without the use of a cold probe, microcoil, or any pre-concentration. Full article

(This article belongs to the Special Issue Marine Natural Products - Advances in Separation, Characterisation and Chemical Profiling Methodologies)

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799 KiB

Open AccessArticle

Five New Secondary Metabolites Produced by a Marine-Associated Fungus, Daldinia eschscholzii

by Zheng-Xi Hu, Yong-Bo Xue, Xiao-Bin Bi, Jin-Wen Zhang, Zeng-Wei Luo, Xiao-Nian Li, Guang-Min Yao, Jian-Ping Wang and Yong-Hui Zhang

Mar. Drugs 2014, 12(11), 5563-5575; https://doi.org/10.3390/md12115563 - 20 Nov 2014

Cited by 34 | Viewed by 7528

Abstract

Five new compounds, including a benzopyran ribonic glycoside, daldiniside A (1), two isocoumarin ribonic glycosides, daldinisides B (2) and C (3), and two alkaloids, 1-(3-indolyl)-2R,3-dihydroxypropan-1-one (4) and 3-ethyl-2, 5-pyrazinedipropanoic acid (5), [...] Read more.

Five new compounds, including a benzopyran ribonic glycoside, daldiniside A (1), two isocoumarin ribonic glycosides, daldinisides B (2) and C (3), and two alkaloids, 1-(3-indolyl)-2R,3-dihydroxypropan-1-one (4) and 3-ethyl-2, 5-pyrazinedipropanoic acid (5), along with five known compounds (6–10), were isolated from the EtOAc extract of the marine-associated fungus, Daldinia eschscholzii. Their structures were elucidated by extensive physicochemical and spectroscopic properties, besides comparison with literature data. The absolute configurations of compounds 1–3 were corroborated by chemical transformation, GC analysis and X-ray crystallographic analysis. Meanwhile, the absolute configuration of compound 4 and the planar structure of compound 6 were also determined based on the X-ray diffraction analysis. The cytotoxicity of compounds 1–10, antifungal and anti-HIV activities of compounds 1–5 and the in vitro assay for glucose consumption of compounds 1–3 were done in the anti-diabetic model, whereas none showed obvious activity. Full article

(This article belongs to the Special Issue Marine Natural Products - Advances in Separation, Characterisation and Chemical Profiling Methodologies)

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323 KiB

Open AccessArticle

Search for Hydrophilic Marine Fungal Metabolites: A Rational Approach for Their Production and Extraction in a Bioactivity Screening Context

by Carine Le Ker, Karina-Ethel Petit, Jean-François Biard and Joël Fleurence

Mar. Drugs 2011, 9(1), 82-97; https://doi.org/10.3390/md9010082 - 10 Jan 2011

Cited by 12 | Viewed by 9106

Abstract

In the search for bioactive natural products, our lab screens hydrophobic extracts from marine fungal strains. While hydrophilic active substances were recently identified from marine macro-organisms, there was a lack of reported metabolites in the marine fungi area. As such, we decided to [...] Read more.

In the search for bioactive natural products, our lab screens hydrophobic extracts from marine fungal strains. While hydrophilic active substances were recently identified from marine macro-organisms, there was a lack of reported metabolites in the marine fungi area. As such, we decided to develop a general procedure for screening of hydrophobic metabolites. The aim of this study was to compare different processes of fermentation and extraction, using six representative marine fungal strains, in order to define the optimized method for production. The parameters studied were (a) which polar solvent to select, (b) which fermentation method to choose between solid and liquid cultures, (c) which raw material, the mycelium or its medium, to extract and (d) which extraction process to apply. The biochemical analysis and biological evaluations of obtained extracts led to the conclusion that the culture of marine fungi by agar surface fermentation followed by the separate extraction of the mycelium and its medium by a cryo-crushing and an enzymatic digestion with agarase, respectively, was the best procedure when screening for hydrophilic bioactive metabolites. During this development, several bioactivities were detected, confirming the potential of hydrophilic crude extracts in the search for bioactive natural products. Full article

(This article belongs to the Special Issue Marine Natural Products - Advances in Separation, Characterisation and Chemical Profiling Methodologies)

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216 KiB

Open AccessArticle

Verrucisidinol and Verrucosidinol Acetate, Two Pyrone-Type Polyketides Isolated from a Marine Derived Fungus, Penicillium aurantiogriseum

by Ke Yu, Biao Ren, Junli Wei, Caixia Chen, Jinsheng Sun, Fuhang Song, Huanqin Dai and Lixin Zhang

Mar. Drugs 2010, 8(11), 2744-2754; https://doi.org/10.3390/md8112744 - 1 Nov 2010

Cited by 34 | Viewed by 10134

Abstract

The new secondary metabolites verrucosidinol (1) and its derivative verrucosidinol acetate (2), together with a potent neurotoxin verrucosidin (3), a congener norverrucosidin (4) and a mixture of two known phytotoxic metabolites terrestric acids (5 [...] Read more.

The new secondary metabolites verrucosidinol (1) and its derivative verrucosidinol acetate (2), together with a potent neurotoxin verrucosidin (3), a congener norverrucosidin (4) and a mixture of two known phytotoxic metabolites terrestric acids (5 and 6), were isolated from the marine derived fungus Penicillium aurantiogriseum. Verrucosidinol has a ring-opened ethylene oxide moiety in the polyene α-pyrone skeleton, and verrucosidinol acetate is its acetate derivative. The chemical structures were determined by comparing with literature data and a combination of spectroscopic techniques, including high resolution mass spectrum and two-dimentional nuclear magnetic resonance spectroscopic analysis. Full article

(This article belongs to the Special Issue Marine Natural Products - Advances in Separation, Characterisation and Chemical Profiling Methodologies)

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Review

Jump to: Research

424 KiB

Open AccessReview

Alternative and Efficient Extraction Methods for Marine-Derived Compounds

by Clara Grosso, Patrícia Valentão, Federico Ferreres and Paula B. Andrade

Mar. Drugs 2015, 13(5), 3182-3230; https://doi.org/10.3390/md13053182 - 21 May 2015

Cited by 169 | Viewed by 12858

Abstract

Marine ecosystems cover more than 70% of the globe’s surface. These habitats are occupied by a great diversity of marine organisms that produce highly structural diverse metabolites as a defense mechanism. In the last decades, these metabolites have been extracted and isolated in [...] Read more.

Marine ecosystems cover more than 70% of the globe’s surface. These habitats are occupied by a great diversity of marine organisms that produce highly structural diverse metabolites as a defense mechanism. In the last decades, these metabolites have been extracted and isolated in order to test them in different bioassays and assess their potential to fight human diseases. Since traditional extraction techniques are both solvent- and time-consuming, this review emphasizes alternative extraction techniques, such as supercritical fluid extraction, pressurized solvent extraction, microwave-assisted extraction, ultrasound-assisted extraction, pulsed electric field-assisted extraction, enzyme-assisted extraction, and extraction with switchable solvents and ionic liquids, applied in the search for marine compounds. Only studies published in the 21st century are considered. Full article

(This article belongs to the Special Issue Marine Natural Products - Advances in Separation, Characterisation and Chemical Profiling Methodologies)

994 KiB

Open AccessReview

Recent Advances and Applications of Experimental Technologies in Marine Natural Product Research

by Ke Li, Yu-Wen Chung-Davidson, Ugo Bussy and Weiming Li

Mar. Drugs 2015, 13(5), 2694-2713; https://doi.org/10.3390/md13052694 - 29 Apr 2015

Cited by 30 | Viewed by 8437

Abstract

Marine natural products are a rich source of novel and biologically active compounds. The number of identified marine natural compounds has grown 20% over the last five years from 2009 to 2013. Several challenges, including sample collection and structure elucidation, have limited the [...] Read more.

Marine natural products are a rich source of novel and biologically active compounds. The number of identified marine natural compounds has grown 20% over the last five years from 2009 to 2013. Several challenges, including sample collection and structure elucidation, have limited the development of this research field. Nonetheless, new approaches, such as sampling strategies for organisms from extreme ocean environments, nanoscale NMR and computational chemistry for structural determination, are now available to overcome the barriers. In this review, we highlight the experimental technology innovations in the field of marine natural products, which in our view will lead to the development of many new drugs in the future. Full article

(This article belongs to the Special Issue Marine Natural Products - Advances in Separation, Characterisation and Chemical Profiling Methodologies)

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1926 KiB

Open AccessReview

Bioactive Dehydrotyrosyl and Dehydrodopyl Compounds of Marine Origin

by Manickam Sugumaran and William E. Robinson

Mar. Drugs 2010, 8(12), 2906-2935; https://doi.org/10.3390/md8122906 - 6 Dec 2010

Cited by 40 | Viewed by 10057

Abstract

The amino acid, tyrosine, and its hydroxylated product, 3,4-dihydroxyphenylalanine (dopa), plays an important role in the biogenesis of a number of potentially important bioactive molecules in marine organisms. Interestingly, several of these tyrosyl and dopa‑containing compounds possess dehydro groups in their side chains. [...] Read more.

The amino acid, tyrosine, and its hydroxylated product, 3,4-dihydroxyphenylalanine (dopa), plays an important role in the biogenesis of a number of potentially important bioactive molecules in marine organisms. Interestingly, several of these tyrosyl and dopa‑containing compounds possess dehydro groups in their side chains. Examples span the range from simple dehydrotyrosine and dehydrodopamines to complex metabolic products, including peptides and polycyclic alkaloids. Based on structural information, these compounds can be subdivided into five categories: (a) Simple dehydrotyrosine and dehydrotyramine containing molecules; (b) simple dehydrodopa derivatives; (c) peptidyl dehydrotyrosine and dehydrodopa derivatives; (d) multiple dehydrodopa containing compounds; and (e) polycyclic condensed dehydrodopa derivatives. These molecules possess a wide range of biological activities that include (but are not limited to) antitumor activity, antibiotic activity, cytotoxicity, antioxidant activity, multidrug resistance reversal, cell division inhibition, immunomodulatory activity, HIV-integrase inhibition, anti-viral, and anti-feeding (or feeding deterrent) activity. This review summarizes the structure, distribution, possible biosynthetic origin, and biological activity, of the five categories of dehydrotyrosine and dehydrodopa containing compounds. Full article

(This article belongs to the Special Issue Marine Natural Products - Advances in Separation, Characterisation and Chemical Profiling Methodologies)

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