Six new linear peptides, pterulamides I-VI (1-6), were isolated from the fruiting bodies of a Malaysian Pterula species. The structures were elucidated by MS and 2D NMR experiments, and the absolute configurations of the constituent amino acids established using Marfey's method. The pterulamides are mainly assembled from nonpolar N-methylated amino acids and, most interestingly, have non-amino-acid N-terminal groups, among them the unusual cinnamoyl, (E)-3-methylsulfinylpropenoyl, and (E)-3-methylthiopropenoyl groups. Furthermore, pterulamides I-V are the first natural peptides with a methylamide C-terminus. Pterulamides I and IV are cytotoxic against the P388 cell line with IC50 values of 0.55 and 0.95 microg/mL (0.79 and 1.33 microM), respectively.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
A new dichlorinated pulvinic acid derivative, methyl-3',5'-dichloro-4,4'-di-O-methylatromentate, was isolated from the fruiting body of a Scleroderma sp. The structure was determined using spectroscopic methods, and an X-ray analysis was carried out for confirmation of the structure. Compound was found to display moderate antimicrobial activity against Bacillus subtilis.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
Three new 5,1'-coupled naphthylisoquinoline alkaloids, ancistrobenomine A (1), 6-O-demethylancistrobenomine A (2), and 5'-O-demethylancistrocline (3), have been isolated from the stem bark of a botanically as yet undescribed highland liana Ancistrocladus sp., proposed to be named "A. benomensis" according to the region in Peninsular Malaysia where it has been discovered on the mountain of Gunung Benom. Two of the compounds possess an unprecedented structure with a novel hydroxymethylene group at C-3 of the fully dehydrogenated isoquinoline moiety. The structural elucidation was achieved by chemical, spectroscopic, and chiroptical methods. As typical of the so-called Ancistrocladaceae type, all of the compounds isolated bear an oxygen at C-6. Biological activities of these alkaloids against different protozoic pathogens are described.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
A new labdane diterpene glucoside, curcumanggoside (1), together with nine known compounds, including labda-8(17),12-diene-15,16-dial (2), calcaratarin A (3), zerumin B (4), scopoletin, demethoxycurcumin, bisdemethoxycurcumin, 1,7-bis(4-hydroxyphenyl)-1,4,6-heptatrien-3-one, curcumin, and p-hydroxycinnamic acid, have been isolated from the rhizomes of Curcuma mangga. Their structures were determined using a combination of 1D (1H NMR, 13C NMR, DEPT) and 2D (COSY, HSQC, HMBC) NMR techniques. All diarylheptanoids and scopoletin showed significant antioxidant activity. Zerumin B, demethoxycurcumin, bisdemethoxycurcumin, and curcumin also exhibited cytotoxic activity against a panel of five human tumor cell lines.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
Phytochemical studies on the rhizomes of Etlingera elatior have resulted in the isolation of 1,7-bis(4-hydroxyphenyl)-2,4,6-heptatrienone (1), demethoxycurcumin (2), 1,7-bis(4-hydroxyphenyl)-1,4,6-heptatrien-3-one (3), 16-hydroxylabda-8(17),11,13-trien-15,16-olide (4), stigmast-4-en-3-one, stigmast-4-ene-3,6-dione, stigmast-4-en-6beta-ol-3-one, and 5alpha,8alpha-epidioxyergosta-6,22-dien-3beta-ol. Compounds 1 and 4 are new, and their structures were elucidated by analysis of spectroscopic data. Diarylheptanoids 1-3 were found to inhibit lipid peroxidation in a more potent manner than alpha-tocopherol.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
From the aerial parts of Atriplex littoralis, three new flavonoid glycosides named atriplexins I-III (1-3), a known flavonoid glycoside, spinacetin 3-O-β-d-glucopyranoside (4), arbutin (5), and 4-hydroxybenzyl-β-d-glucopyranoside (6) were isolated. Their structures were elucidated on the basis of detailed spectroscopic analysis, including 1D and 2D NMR (COSY, NOESY, TOCSY, HSQC, HMBC) and HRESITOF MS data. The compounds were tested for in vitro protective effects on chromosome aberrations in peripheral human lymphocytes using a cytochalasin-B-blocked micronucleus (MN) assay in a concentration range of 0.8-7.4 μM of final culture solution. Chromosomal damage was induced by 2 Gy of γ-radiation on binucleated human lymphocytes, and the effects of the compounds were tested 2 to 19 h after irradiation. The frequency of micronuclei (MNi) was scored in binucleated cells, and the nuclear proliferation index was calculated. The highest prevention of in vitro biochemical and cytogenetic damage of human lymphocytes induced by γ-radiation was exhibited by 3 (reduction of MN frequency by 31%), followed by 4 and 6.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
The Ricinus communis biomarker peptides RCB-1 to -3 comprise homologous sequences of 19 (RCB-1) or 18 (RCB-2 and -3) amino acid residues. They all include four cysteine moieties, which form two disulfide bonds. However, neither the 3D structure nor the biological activity of any of these peptides is known. The synthesis of RCB-1, using microwave-assisted, Fmoc-based solid-phase peptide synthesis, and a method for its oxidative folding are reported. The tertiary structure of RCB-1, subsequently established using solution-state NMR, reveals a twisted loop fold with antiparallel β-sheets reinforced by the two disulfide bonds. Moreover, RCB-1 was tested for antibacterial, antifungal, and cytotoxic activity, as well as in a serum stability assay, in which it proved to be remarkably stable.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
Four new 2,3-secodammarane triterpenoids, stellatonins A-D (3-6), together with a new 3,4-secodammarane triterpenoid, stellatonin E (7), and the known silvestrol (1), 5‴-episilvestrol (2), and β-sitosterol, were isolated from a methanol extract of the stems of Aglaia stellatopilosa through bioassay-guided fractionation. The structures of the new compounds were elucidated using spectroscopic and chemical methods. The compounds were evaluated for their cytotoxic activity against three human cancer cell lines and for their antimicrobial activity using a microtiter plate assay against a panel of Gram-positive and Gram-negative bacteria and fungi.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
A large-scale in vitro screening of tropical plants using an antibacterial assay permitted the selection of several species with significant antibacterial activities. Bioassay-guided purification of the dichloromethane extract of the leaves of the Malaysian species Vitex vestita, led to the isolation of six new labdane-type diterpenoids, namely, 12-epivitexolide A (2), vitexolides B and C (3 and 4), vitexolide E (8), and vitexolins A and B (5 and 6), along with six known compounds, vitexolides A (1) and D (7), acuminolide (9), 3β-hydroxyanticopalic acid (10), 8α-hydroxyanticopalic acid (11), and 6α-hydroxyanticopalic acid (12). Their structures were elucidated on the basis of 1D and 2D NMR analyses and HRMS experiments. Both variable-temperature NMR spectroscopic studies and chemical modifications were performed to investigate the dynamic epimerization of the γ-hydroxybutenolide moiety of compounds 1-4. Compounds were assayed against a panel of 46 Gram-positive strains. Vitexolide A (1) exhibited the most potent antibacterial activity with minimal inhibitory concentration values ranging from 6 to 96 μM, whereas compounds 2 and 6-9 showed moderate antibacterial activity. The presence of a β-hydroxyalkyl-γ-hydroxybutenolide subunit contributed significantly to antibacterial activity. Compounds 1-4 and 6-9 showed cytotoxic activities against the HCT-116 cancer cell line (1 < IC50s < 10 μM) and human fetal lung fibroblast MRC5 cell line (1 < IC50s < 10 μM for compounds 1, 2, 7, 8, and 9).
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
In an ongoing program to identify new anti-infective leads, an extract derived from whole plant material of Desmodium congestum collected in the Sarawak rainforest was found to have anti-MRSA activity. Bioassay-guided isolation led to the isolation of two new prenylated chalcones, 5'-O-methyl-3-hydroxyflemingin A (1) and 5'-O-methylflemingin C (2), which were closely related to the flemingins previously isolated from various Flemingia species. Chalcones 1 and 2, which were determined to be 4:6 enantiomeric mixtures by chiral HPLC, exhibited moderate activity against a panel of Gram-positive bacteria and were also cytotoxic to the HEK293 human embryonic kidney cell line.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
Methanolic extracts of the leaves, stems, and roots of Phyllagathis rotundifolia collected in Malaysia yielded seven galloylated cyanogenic glucosides based on prunasin, with six of these being new compounds, prunasin 2',6'-di-O-gallate (3), prunasin 3',6'-di-O-gallate (4), prunasin 4',6'-di-O-gallate (5), prunasin 2',3',6'-tri-O-gallate (6), prunasin 3',4',6'-tri-O-gallate (7), and prunasin 2',3',4',6'-tetra-O-gallate (8). Also obtained was a new alkyl glycoside, oct-1-en-3-yl alpha-arabinofuranosyl-(1-->6)-beta-glucopyranoside (9). For compounds 3-8, the galloyl groups were individually linked to the sugar moieties via ester bonds. All new structures were established on the basis of NMR and MS spectroscopic studies. In addition, prunasin (1), gallic acid and its methyl ester, beta-glucogallin, 3,6-di-O-galloyl-D-glucose, 1,2,3,6-tetra-O-galloyl-beta-D-glucose, strictinin, 6-O-galloyl-2,3-O-(S)-hexahydroxydiphenoyl-D-glucose, praecoxin B, and pterocarinin C were isolated and identified. The isolation of 1 and its galloyl derivatives (3-8) from a Melastomataceous plant are described for the first time.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
Six new sulfur-containing bis-iridoid glucosides, saprosmosides A-F (1-6), were isolated from the leaves of Saprosma scortechinii. From the stems of this same plant, two new iridoid glucosides, 3,4-dihydro-3-methoxypaederoside (8) and 10-O-benzoyldeacetylasperulosidic acid (12), were isolated. Their structures were elucidated by means of chemical, NMR, and mass spectroscopic methods. Additionally, 11 known iridoid glucosides were isolated and characterized as deacetylasperuloside, asperuloside, paederoside (7), deacetylasperulosidic acid (9), scandoside, asperulosidic acid, 10-acetylscandoside, paederosidic acid (10), 6-epi-paederosidic acid (11), methylpaederosidate, and monotropein. The structures of the new bis-iridoid glucosides were formed by intermolecular esterification between the glucose and carboxyl groups of three monomeric iridoid glucosides (7, 9, and 10).
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
Five new indole alkaloids of the ibogan type (1-5), in addition to 12 other known iboga alkaloids, were obtained from the leaf and stem-bark extract of the Malayan species Tabernaemontana corymbosa, viz., 19(S)-hydroxyibogamine (1), 19-epi-isovoacristine (2), isovoacryptine (3), 3R/S-ethoxyheyneanine (4), and 3R/S-ethoxy-19-epi-heyneanine (5). The structures were determined using NMR and MS analysis and comparison with known related compounds.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
Two new resveratrol tetramers, hopeaphenol A (1) and isohopeaphenol A (2), along with the known vaticaphenol A (3), were isolated from the stem bark of Vatica oblongifolia ssp. oblongifolia through bioassay-guided fractionation. The structures and their relative stereochemistry were determined by spectroscopic techniques. Compounds 1 and 3 demonstrated moderate activity against methicillin-resistant Staphylococcus aureus and Mycobacterium smegmatis.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
Ten new bisindole alkaloids of the vobasinyl-ibogan type, viz., conodiparines A-F (1-6), conodutarines A and B (7, 8), and cononitarines A and B (9, 10), were obtained from the leaf extract of the Malayan species Tabernaemontana corymbosa. The structures were determined using NMR and MS analysis.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
Ten new indole alkaloids, alstomaline (1), 10,11-dimethoxynareline (2), alstohentine (3), alstomicine (4), 16-hydroxyalstonisine (5), 16-hydroxyalstonal (6), 16-hydroxy-N(4)-demethylalstophyllal oxindole (7), alstophyllal (8), 6-oxoalstophylline (9), and 6-oxoalstophyllal (10), in addition to 21 other known ones, were obtained from the leaf extract of the Malayan Alstonia macrophylla. The structures were determined using NMR and MS analysis.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
Chemical investigation of the organic extract from Moorea bouillonii, collected in Sabah, Malaysia, led to the isolation of three new chlorinated fatty acid amides, columbamides F (1), G (2), and H (3). The planar structures of 1-3 were established by a combination of mass spectrometric and NMR spectroscopic analyses. The absolute configuration of 1 was determined by Marfey's analysis of its hydrolysate and chiral-phase HPLC analysis after conversion and esterification with Ohrui's acid, (1S,2S)-2-(anthracene-2,3-dicarboximido)cyclohexanecarboxylic acid. Compound 1 showed biosurfactant activity by an oil displacement assay. Related known fatty acid amides columbamide D and serinolamide C exhibited biosurfactant activity with critical micelle concentrations of about 0.34 and 0.78 mM, respectively.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
Reexamination of the absolute configuration of recently isolated eburnane alkaloids from Malaysian Kopsia and Leuconotis species by X-ray diffraction analysis and ECD/TDDFT has revealed the existence of biosynthetic enantiodivergence. Three different scenarios are discerned with respect to the composition of the enantiomeric eburnane alkaloids in these plants: first, where the new eburnane congeners possess the same C-20, C-21 absolute configurations as the common eburnane alkaloids (eburnamonine, eburnamine, isoeburnamine, eburnamenine) occurring in the same plant; second, where the new eburnane congeners possess opposite or enantiomeric C-20, C-21 absolute configurations compared to the common eburnane alkaloids found in the same plant; and, third, where the four common eburnane alkaloids were isolated as racemic or scalemic mixtures, while the new eburnane congeners were isolated as pure enantiomers with a common C-20, C-21 configuration (20α, 21α). Additionally, the same Kopsia species (K. pauciflora) found in two different geographical locations (Peninsular Malaysia and Malaysian Borneo) showed different patterns in the composition of the enantiomeric eburnane alkaloids. Revision of the absolute configurations of a number of new eburnane congeners (previously assigned based on the assumption of a common biogenetic origin to that of the known eburnane alkaloids co-occurring in the same plant) is required based on the present results.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
Tengerensine (1), isolated as a racemate and constituted from a pair of bis-benzopyrroloisoquinoline enantiomers, and tengechlorenine (2), purified as a scalemic mixture and constituted from a pair of chlorinated phenanthroindolizidine enantiomers, were isolated from the leaves of Ficus fistulosa var. tengerensis, along with three other known alkaloids. The structures of 1 and 2 were determined by spectroscopic data interpretation and X-ray diffraction analysis. The enantiomers of 1 were separated by chiral-phase HPLC, and the absolute configurations of (+)-1 and (-)-1 were established via experimental and calculated ECD data. Compound 1 is notable in being a rare unsymmetrical cyclobutane adduct and is the first example of a dimeric benzopyrroloisoquinoline alkaloid, while compound 2 represents the first naturally occurring halogenated phenanthroindolizidine alkaloid. Compound (+)-1 displayed a selective in vitro cytotoxic effect against MDA-MB-468 cells (IC50 7.4 μM), while compound 2 showed pronounced in vitro cytotoxic activity against all three breast cancer cell lines tested (MDA-MB-468, MDA-MB-231, and MCF7; IC50 values of 0.038-0.91 μM).
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular
A novel microgels were polymerized using styrene (St), methyl methacrylate (MMA), acrylamide (AAm), and acrylic acid (AAc) monomers in the presence of N,N'-methylenebisacrylamide (MBA) cross-linker. Pre-emulsified monomer was first prepared followed by polymerizing monomers using semi-batch emulsion polymerization. Fourier Transform Infrared Spectroscopy (FTIR) and (1)H Nuclear Magnetic Resonance (NMR) were used to determine the chemical structure and to indentify the related functional group. Grafting and cross-linking of poly(acrylamide-co-acrilic acid)-grafted-poly(styrene-co-methyl methacrylate) [poly(AAm-co-AAc)-g-poly(St-co-MMA)] microgels are approved by the disappearance of band at 1300 cm(-1), 1200 cm(-1) and 1163 cm(-1) of FTIR spectrum and the appearance of CH peaks at 5.5-5.7 ppm in (1)H NMR spectrum. Scanning Electron Microscope (SEM) images indicated that poly(St-co-MMA) particle was lobed morphology coated by cross-linked poly(AAm-co-AAc) shell. Furthermore, SEM results revealed that poly(AAm-co-AAc)-g-poly(St-co-MMA) is composite particle that consist of "raspberry"-shape like structure core. Internal structures of the microgels showed homogeneous network of pores, an extensive interconnection among pores, thicker pore walls, and open network structures. Water absorbency test indicated that the sample with particle size 0.43 μm had lower equilibrium water content, % than the sample with particle size 7.39 μm.
Matched MeSH terms: Nuclear Magnetic Resonance, Biomolecular