Three novel quassinoids, javanicolides A and B, and javanicoside A, from seeds of Brucea javanica

Two novel quassinoids, javanicolides A and B, and one novel quassinoid glucoside, javanicoside A were isolated from the seeds of Brucea javanica Merr. (Simaroubaceae), along with four known quassinoids, yadanziolides A and D, and bruceins D and E, and two known quassinoid glucosides, yadanziosides D and L. Their structures were elucidated by the analysis of spectral data and chemical evidence.     

Kororamide A,a new tribrominated indole alkaloid from the Australian bryozoan Amathia tortuosa

A new tribrominated indole alkaloid, kororamide A together with the known alkaloid convolutamine F, were isolated through the application of mass directed purification from the bryozoan, Amathia tortuosa collected from northern New South Wales, Australia. The structure of kororamide A was deduced from the analysis of 1D/2D NMR and MS data. Kororamide A exists in solution as a mixture of interconverting cis–trans amide regioisomers in a ratio of 4:5. Bioactivity testing demonstrated that kororamide A was marginally active against chloroquine-sensitive and resistant strains of the malarial parasite Plasmodium falciparum, and was inactive against normal human cell lines.     

Trigonoines A and B, two novel alkaloids from the leaves of Trigonostemon lii

Two novel alkaloids, trigonoine A containing a 2,8-diazabicyclo[3.3.1]nonane ring system and trigonoine B formed by a combination of a 2,3-dihydroquinolin-4-one and 3H-pyrrolo[2,3-c]quinoline rearranged from β-carboline skeleton were isolated from the leaves of Trigonostemon lii. Their structures were elucidated by 1D and 2D NMR spectroscopic methods.     

Cyclic diarylheptanoids deoxycymodienol and isotedarene A from Zostera marina (Zosteraceae)

A first phytochemical investigation of apolar natural products of the seagrass Zostera marina L. (Zosteraceae) yielded cymodienol, a cyclic diarylheptanoid so far only known from the seagrass Cymodocea nodosa (Ucria) Asch. (Cymodoceaceae) and a previously undescribed diaryheptanoid, isotedearene A, which is closely related to tedarene A, a natural product previously described from the neotropic sponge Tedania ignis (Duchassaing & Michelotti, 1864) (Tedaniidae). Structures were established by mass spectrometry and extensive 1D and 2D NMR experiments.     

Chloramultilide A, a highly complex sesquiterpenoid dimmer from Chloranthus multistachys

A highly complex sesquiterpenoid dimmer, chloramultilide A (1), was isolated from Chloranthus multistachys. Its structure and relative stereochemistry were mainly established by using 1D NMR and 2D NMR spectra.     

Drimane-Type Sesquiterpenoids Derived from the Tropical Basidiomycetes Perenniporia centrali-africana and Cerrena sp. nov

Five new drimane-type sesquiterpenoids were isolated from cultures of the tropical basidiomycetes, Perenniporia centrali-africana (originating from Kenya) and Cerrena sp. nov. (originating from Thailand). A new pereniporin A derivative (1), a new drimane-type sesquiterpene lactam (2), and the new 6,7-Dehydro-isodrimenediol (3) were isolated from P. centrali-africana. In parallel, the two new drimane-type sesquiterpene lactams 5 and 6 were isolated together with known isodrimenediol (4) from Cerrena sp. This is the first report of drimane-type sesquiterpene lactams from basidiomycetes. The structures were elucidated based on 1D and 2D nuclear magnetic resonance (NMR) spectroscopic data, in combination with high-resolution electrospray mass spectrometric (HR-ESIMS) data. The compounds were devoid of significant antimicrobial and cytotoxic activities.     

Fusaspirols A-D,novel oxaspirol derivatives isolated from Fusarium solani B-18

Four novel compounds with γ-methylidene-spirobutanolide core, fusaspirols A-D, were isolated from the brown rice culture of Fusarium solani B-18. Their structures were established by extensive spectroscopic analyses of 1D/2D-NMR, HRESITOFMS, and chemical derivatization. The absolute configurations of secondary alcohols in fusaspirols A and D were determined using modified Mosher's ester method. Fusaspirol A and 4,9-di-O-acetylfusaspirol A activated a signaling pathway in osteoclastic differentiation of murine macrophage derived RAW264.7?cells.     

Cebulactams A1 and A2, new macrolactams isolated from Saccharopolyspora cebuensis, the first obligate marine strain of the genus Saccharopolyspora

The new macrolactams cebulactams A1 and A2 were isolated from an extract of the first obligate marine strain of the genus Saccharopolyspora. Their constitutionally identical structures, each bearing a six-membered cyclic ether as part of the macrocycle, and their relative configurations were elucidated by MS methods and by 1D and 2D NMR techniques.     

Britanlins A-D, four novel sesquiterpenoids from Inula britannica

A phytochemical investigation on the flowers of Inula britannica has led to the isolation of four novel sesquiterpenoids, britanlins A-D. Britanlins A-C feature the rare presilphiperfolane-type frameworks, which play an important role in biogenesis of triquinane sesquiterpenoids. Britanlin D possessed a rearranged pseudoguaiane skeleton, which was first isolated from nature. The structures of britanlins A to D were elucidated on the basis of extensive spectroscopic methods. The structures of britanlins A and D were further confirmed by single crystal X-ray diffraction.     

Two New Triterpenes from Basidiomata of the Medicinal and Edible Mushroom,Laetiporus sulphureus

In the search for novel anti-infectives from natural sources, fungi, in particular basidiomycetes, have proven to still harbor so much potential in terms of secondary metabolites diversity. There have been numerous reports on isolating numerous secondary metabolites from genus Laetiporus. This study reports on two new triterpenoids, laetiporins C and D, and four known triterpenes from the fruiting body of L. sulphureus. The structures of the isolated compounds were elucidated based on their 1D and 2D nuclear magnetic resonance (NMR) spectroscopic data in combination with high-resolution electrospray mass spectrometric (HR-ESIMS) data. Laetiporin C exhibited weak antifungal activity against Mucor hiemalis. Furthermore, the compounds showed weak antiproliferative activity against the mouse fibroblast L929 and human cancer cell lines, including KB-3-1, A431, MCF-7, PC-3 and A549.     

Cytosporones O, P and Q from an endophytic Cytospora sp.

Cytosporones O, P and Q, together with the known compounds cytosporones B, C, D, E and dothiorelones A, B, C, and H were isolated from the ascomycete fungus Cytospora sp. during a chemotaxonomic study of fungal endophytes belonging to the related genera Cytospora and Phomopsis from Brazil. The structures were determined by NMR spectroscopy and mass spectrometry. With exception of cytosporones D, E, Q, and dothiorelone B, all compounds were consistently detected in the metabolite profiles of eight Cytospora isolates investigated; and were also produced by a distinct chemotype of Phomopsis.     

Pennelliiside D,a New Acyl Glucose from Solanum pennellii and Chemical Synthesis of Pennelliisides

Acyl glucoses are a group of specialized metabolites produced by Solanaceae. Solanum pennellii, a wild-type tomato plant, produces acyl glucoses in its hair-like epidermal structures known as trichomes. These compounds have been found to be herbicides, microbial growth inhibitors, or allelopathic compounds. However, there are a few reports regarding isolation and investigation of biological activities of acyl glucoses in its pure form due to the difficulty of isolation. Here, we report a new acyl glucose, pennelliiside D, isolated and identified from S. pennellii. Its structure was determined by 1D NMR and 2D NMR, together with FD-MS analysis. To clarify the absolute configuration of the acyl moiety of 2-methylbutyryl in the natural compound, two possible isomers were synthesized starting from β-D-glucose pentaacetate. By comparing the spectroscopic data of natural and synthesized compounds of isomers, the structure of pennelliiside D was confirmed to be 3,4-O-diisobutyryl-2-O-((S)-2-methylbutyryl)-D-glucose. Pennelliiside D and its constituent fatty acid moiety, (S)-2-methylbutanoic acid, did not show root growth-inhibitory activity. Additionally, in this study, chemical synthesis pathways toward pennelliisides A and B were adapted to give 1,6-O-dibenzylpennelliisides A and B.     

Two novel norlignans from Gymnotheca chinensis

Two novel norlignans, gymnothedelignans A and B were isolated from the whole plants of Gymnotheca chinensis. These norlignans possess a rare 2/5 epoxy benzocycloheptanone skeleton. Their structures were established on the basis of 1D and 2D NMR spectral data analysis, and the absolute stereochemistry of gymnothedelignans A and B was further confirmed by single crystal X-ray diffraction analysis.     

Total synthesis of infectopyrone,aplysiopsenes A–C,ent-aplysiopsene D,phomapyrones A and D, 8,9-dehydroxylarone,and nectriapyrone

The total synthesis of the 2-pyrone natural products nectriapyrone, aplysiopsenes A–C, ent-aplysiopsene D, phomapyrones A and D, and of 8,9-dehydroxylarone were achieved by Wittig olefination starting with vermopyrone. Infectopyrone was synthesized by Horner–Wadsworth–Emmons reaction starting with phomapyrone D. Racemic phomapyrone C methyl ether was obtained by hydrogenation of nectriapyrone. The total syntheses were achieved starting from commercially available 3,5-heptanedione and led to the desired natural products in 18–46% over 5–6 steps, whereupon all five-step syntheses were carried out with a single chromatographic workup. The total synthesis of infectopyrone, aplysiopsenes A–D, of phomapyrones A and D, and of 8,9-dehydroxylarone were achieved for the first time, giving unambiguous proof for the proposed structures of these natural products.     

New azaphilones from Chaetomium globosum isolated from the built environment

A strain of Chaetomium globosum (DAOM 240359) was isolated from an indoor air sample in Ottawa, Ontario, Canada. When fermented in liquid culture, this strain produced a number of known metabolites including chaetoglobosins A (6), C, and F (7), chaetomugilin D (5), chaetoviridin A (4), and three new nitrogenous azaphilones; 4′-epi-N-2-hydroxyethyl-azachaetoviridin A (1), N-2-butyric-azochaetoviridin E (2), and isochromophilone XIII (3). The structures were elucidated by spectroscopic analysis including; HRMS, 1D and 2D NMR, UV, and ORD. Compounds 2–7 were antimicrobial when tested using quantitative growth inhibition assays.     

A novel 10-membered macrocyclic lactone from the mangrove-derived endophytic fungus Annulohypoxylon sp.

A novel 10-membered macrolactone, hypoxylide (1), was isolated from the endophytic fungus Annulohypoxylon sp. that was obtained from the Mangrove plant Rhizophora racemosa. The structure and absolute configuration of 1 were unambiguously elucidated by comprehensive 1D and 2D NMR, as well as by HRESIMS and ECD spectroscopic analyses. Hypoxylide (1) features an unprecedented polyketide skeleton comprised of a trihydroxynaphthalene-dione moiety fused to a decalactone ring. A plausible biosynthetic pathway of this novel metabolite is proposed.     

Secondary Metabolites and Their Cytotoxic Activity of Artemisia nitrosa Weber. and Artemisia marschalliana Spreng.

As a promising source of biologically active substances, the Artemisia species from Kazakhstan have not been investigated efficiently. Considering the rich history, medicinal values, and availability of the Artemisia plants, systematic investigations of two Artemisia species growing in the East Kazakhstan region were conducted. In this study, one new germacrane-type sesquiterpene lactone (11), together with 10 known sesquiterpenes and its dimer, were characterized from A. nitrosa Weber. Additionally, one new chromene derivative (1’) with another 12 known compounds, including coumarins, sesquiterpene diketones, phenyl propanoids, polyacetylenics, dihydroxycinnamic acid derivatives, fatty acids, naphthalene derivatives, flavones, and caffeic acid derivatives were isolated from A. marschalliana Spreng. All compounds were isolated and identified for the first time from these two Artemisia species. The structures of new compounds (11, 1’) were established by using UV, TOFMS, LC–MS, 1D and 2D NMR spectroscopic analyses. The cytotoxicity of all isolated compounds was evaluated. As a result, all compounds did not show significant inhibition against HL-60 and A-549 cell lines. The sesquiterpenoids isolated from A. nitrosa were tested for their inhibitory activity against the LPS-induced NO release from the RAW624.7 cells, and neither of them exhibited significant activity.     

Evidence Showing Duplication and Recombination of cel Genes in Tandem from Hyperthermophilic Thermotoga sp.

This study was conducted to assess the gene duplication and diversification of tandem cellulase genes in thermophilic bacteria. The tandem cellulase genes cel5C and cel5D were cloned from Thermotoga maritima MSB8, and a survey of the thermophilic bacterial genome for tandem cel genes from the databases was carried out. A clone having 2.3?kb fragment from T. maritima MSB8 showed cellulase activity, which had two open reading frames in tandem (cel5C and cel5D). The cel5C gene has 954?bp, which encodes a protein of 317 amino acid residues with a signal peptide of 23 amino acids, and the other gene cel5D consisting of 990?bp encoding a protein of 329 amino acid residues. These two proteins have similarity with the enzymes of glycosyl hydrolase family 5. From the enzyme assay, it was observed that Cel5C was extracellular and Cel5D was intracellular cellulase. Phylogenetic and homology matrix analyses of DNA and protein sequences revealed that family 12 cellulase enzymes Cel12A and Cel12B displayed higher homology (>50?%), but Cel5C and Cel5D enzymes belong to family 5 displayed lower homology (<30?%). In addition, repeated and mirror sequences in tandem genes are supposed to show the existence of gene duplication and recombination.     

Sulfur-containing and dimeric flavanols from Glycosmis montana

Two novel sulfur-containing flavanols, glymontanines A and B, and two new flavanol dimers, montahomobisflavans A and B, were isolated from the twigs and leaves of Glycosmis montana. Their structures were elucidated by spectroscopic methods including 2D NMR analysis.     

Novel pyridino-α-pyrone sesquiterpene type pileotin produced by a sea urchin-derived Aspergillus sp.

A new metabolite, pileotin A, was isolated from a strain of Aspergillus fumigatus originally obtained from the sea urchin Toxopneustes pileolus together with the known compound oxalicine B. The relative stereostructure of pileotin A was elucidated based on spectroscopic analyses, including 1D and 2D NMR techniques. This unique pyridino-α-pyrone sesquiterpene type metabolite has spiro-δ-lactone at C-4.