Structures of novel epipolythiodioxopiperazines, emethallicins B, C, and D, potent inhibitors of histamine release, from Emericella heterothallica

Novel compounds designated emethallicins B (1), C (2), and D (3), along with emethallicin A (4), were isolated from the mycelium of the heterothallic fungus, Emericella heterothallica (mating type a). The structures of emethallicins B (1), C (2), and D (3) were determined on the basis of spectroscopic and chemical investigations. Emethallicins B (1) and C (2) are epitetrathiodioxopiperazines, which have the same basic carbon skeleton as apoaranotin (19) and acetylaranotin (17), respectively, whereas emethallicin D (3) is an epitrithiodioxopiperazine derivative, which has the same carbon skeleton as apoaranotin (19). It is very interesting that a large amount of the disulfide, emethallicin A (4), was isolated from the strain of mating type A and that the corresponding tetrasulfide, emethallicin B (1), and trisulfide, emethallicin D (3), were isolated from the other mating type strain, along with a small amount of the disulfide (4). Emethallicins B (1), C (2), and D (3) have potent inhibitory activity against compound 48/80-induced histamine release from mast cells, like emethallicin A (4).     

Medicinal flowers. XXI. Structures of perennisaponins A, B, C, D, E, and F, acylated oleanane-type triterpene oligoglycosides, from the flowers of Bellis perennis

Six new acylated oleanane-type triterpene oligoglycosides, perennisaponins A (1), B (2), C (3), D (4), E (5), and F (6), were isolated from the flowers of Bellis perennis (Daisy flower) together with 14 saponins, nine flavonoids, and two glycosides. The structures of 1-6 were elucidated on the basis of chemical and physicochemical evidence.     

Medicinal Flowers. XXXII. Structures of oleanane-type triterpene saponins, perennisosides VIII, IX, X, XI, and XII, from the flowers of Bellis perennis

Five new triterpene saponins perennisosides VIII (1), IX (2), X (3), XI (4), and XII (5) were isolated from the MeOH-eluated fraction of the methanolic extract from the flowers of Bellis perennis. The MeOH-eluted fraction of the methanolic extract from the flowers of B. perennis was found to inhibit gastric emptying in olive oil-loaded mice at a dose of 200 mg/kg, per os (p.o.). The stereostructures of 1-5 were elucidated on the basis of chemical and spectroscopic evidence.     

Three new quassinoids,ailantinol E,F, and G,from Ailanthus altissima

Three new quassinoids, ailantinol E (1), ailantinol F (2), and ailantinol G (3), and related compounds were isolated from Ailanthus altissima grown in Taiwan. Their structures were elucidated from spectral evidence. Each new quassinoid was evaluated for its antitumor promoting effects against Epstein-Barr virus early antigen activation introduced by 12-O-tetradecanoylphorbol-13-acetate in Raji cells. The new quassinoids were found to show potent activity without showing any cytotoxicity. The screening for inhibitors against nitric oxide donor action was also conducted using the new quassinoids and some standard samples.     

Araguspongines B, C, D, E, F, G, H, and J, new vasodilative bis-1-oxaquinolizidine alkaloids from an okinawan marine sponge, Xestospongia sp

Nine new vasodilative alkaloids, araguspongines A, B (1), C (2), D (3), E (4), F (5), G (6), H (7), and J (8), were isolated from an Okinawan marine sponge, Xestospongia sp. On the basis of chemical and physicochemical evidence, the absolute stereostructures of araguspongines B, D, E, F, G, H, and J were determined respectively as 1, 3, 4, 5, 6, 7, 8, and the relative stereostructure of araguspongine C was determined as 2 having two 1-oxaquinolizidine moieties. Araguspongines B, D, and E each comprised a pair of the enantiomers, 1a and 1b, 3a and 3b, and 4a and 4b, respectively.     

Determination of benomyl, diphenyl, o-phenylphenol, thiabendazole, chlorpyrifos, methidathion, and methyl parathion in oranges by solid-phase extraction, liquid chromatography, and gas chromatography

A simple and rapid method was developed for determination of benomyl, diphenyl (DP), o-phenylphenol (OPP), thiabendazole (TBZ), chlorpyrifos, methidathion, and methyl parathion in whole oranges. These compounds were extracted from a mixture of samples and anhydrous sodium acetate with ethyl acetate. The ethyl acetate extract was concentrated and cleaned up by passing through tandem solid-phase extraction columns consisting of anion-exchange and primary/secondary amine bonded silica. The eluate was concentrated and volume was adjusted with methanol for subsequent liquid chromatography (LC) and gas chromatography (GC). Benomyl (as methyl-2-benzimidazole carbamate, MBC), DP, OPP, and TBZ residues were determined by LC with fluorescence detection. Recoveries at 3 fortified levels (0.1, 1, and 10 micrograms/g) ranged from 63.9 to 97.4%, with coefficients of variation (CVs) of 1.6 to 15.5%. Limits of detection (LODs) were 0.01 microgram/g for DP, OPP, TBZ and 0.05 microgram/g for benomyl. Chlorpyrifos, methidathion, and methyl parathion residues were determined by GC with flame photometric detection. Recoveries ranged from 90.4 to 97.0%, with CVs of 2.1 to 5.9%. LODs were 0.005 microgram/g for chlorpyrifos and methyl parathion, and 0.01 microgram/g for methidathion.     

Preparation of iron,aluminium, calcium,magnesium, and zinc humates for environmental applications

A few non-conventional humate sorbents, i.e. iron humate (FeH), aluminium humate (AlH), calcium humate (CaH), magnesium humate (MgH), and zinc humate (ZnH), were prepared from a commercial product Fortehum L/K (Humatex, Bílina, Czech Republic). The metal content in humates was determined by X-ray fluorescence analysis, the organic elements (C, H, N, and S) were analysed by an Elementar Vario III and the functional groups were determined by classical methods using KBr pellets and diffuse reflection infrared spectroscopy (DRIFTS). FeH, AlH, and ZnH were tested as sorbents for the removal of inorganic or organic pollutants (metals, inorganic ions, dyes, and chlorophenols) from waste water. Sorption properties decreased in order: ZnH, AlH, FeH. CaH and MgH are partly soluble and therefore they are not usable as sorbents. However, their ion-exchange abilities for heavy metals are excellent which makes them usable for phytoremediation and bioremediation.     

Atomic absorption spectrometric determination of chromium, copper, lead, mercury, and zinc in sediments collected in Bayou d'Inde, southwestern Louisiana

The concentrations of the metals chromium (Cr), copper (Cu), lead (Pb), mercury (Hg), and zinc (Zn) were determined in sediment cores taken from Bayou d'Inde in southwestern Louisiana. Previous studies had reported elevated concentrations of these trace metals in sediments along this waterway. The current study, conducted more than a decade later, was designed to determine if these metals had migrated from the areas of highest concentrations. Concentrations as high as 400 mg/kg for Cr, 1100 mg/kg for Cu, 10 mg/kg for Hg, and 600 mg/kg for Pb and Zn were found. Areas of high concentrations of metals were isolated within a distance of about 1 km from the most highly contaminated areas in the bayou. Low concentrations of metals were found at the mouth of the bayou. Estimated sedimentation rates of 0.67-1.2 cm/yr were based on the burial of the sediments originally studied. The concentrations of the metals studied remained high and were also highly localized, both spatially and temporally.     

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.     

地耳苯抗疟有效成份的研究—地耳苯系A、B、C、D的分离和结构

从地耳草中分离到四个间苯三酚衍生物, 定名为地耳草素A、B、C、D. 通过紫外、红外、核磁和质谱分析以及化学反应, 推定其结构分别为4、8、12和14. 4和8对鼠疟原虫有显著抑制作用.     

High-throughput simultaneous analysis of buprenorphine, methadone, cocaine, opiates, nicotine, and metabolites in oral fluid by liquid chromatography tandem mass spectrometry

A method for simultaneous determination of buprenorphine (BUP), norbuprenorphine (NBUP), methadone, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), cocaine, benzoylecgonine (BE), ecgonine methyl ester (EME), anhydroecgonine methyl ester (AEME), morphine, codeine, 6-acetylmorphine (6AM), heroin, 6-acetylcodeine (6AC), nicotine, cotinine, and trans-3′-hydroxycotinine (OH-cotinine) by liquid chromatography tandem mass spectrometry in oral fluid (OF) was developed and extensively validated. Acetonitrile (800 μL) and OF (250 μL) were added to a 96-well Isolute-PPT+protein precipitation plate. Reverse-phase separation was achieved in 16 min and quantification was performed by multiple reaction monitoring. The assay was linear from 0.5 or 1 to 500 μg/L. Intraday, interday, and total imprecision were less than 13% (n?=?20), analytical recovery was 92–114% (n?=?20), extraction efficiencies were more than 77% (n?=?5), and process efficiencies were more than 45% (n?=?5). Although ion suppression was detected for EME, cocaine, morphine, 6AC, and heroin (less than 56%) and enhancement was detected for BE and nicotine (less than 316%), deuterated internal standards compensated for these effects. The method was sensitive (limit of detection 0.2–0.8 μg/L) and specific (no interferences) except that 3-hydroxy-4-methoxyamphetamine interfered with AEME. No carryover was detected, and all analytes were stable for 24 h at 22 °C, for 72 h at 4 °C, and after three freeze–thaw cycles, except cocaine, 6AC, and heroin (22–97% loss). The method was applied to 41 OF specimens collected throughout pregnancy with a Salivette® OF collection device from an opioid-dependent BUP-maintained pregnant woman. BUP ranged from 0 to 7,400 μg/L, NBUP from 0 to 71 μg/L, methadone from 0 to 3 μg/L, nicotine from 32 to 5,020 μg/L, cotinine from 125 to 508 μg/L, OH-cotinine from 11 to 51 μg/L, cocaine from 0 to 419 μg/L, BE from 0 to 351 μg/L, EME from 0 to 286 μg/L, AEME from 0 to 7 μg/L, morphine from 0 to 22 μg/L, codeine from 0 to 1 μg/L, 6AM from 0 to 4 μg/L, and heroin from 0 to 2 μg/L. All specimens tested negative for EDDP and 6AC. This method permits a fast and simultaneous quantification of 16 drugs and metabolites in OF, with good selectivity and sensitivity.     

Stoloniferone-a, -b, -c,and -d,four new cytotoxic steroids from the okinawan soft coral clavularia viridis

Four new cytotoxic steroids named stoloniferone-a (7a), -b (7b), -c (7c), and -d (7d) were isolated from the stoloniferan Okinawan soft coral Clavularia viridis and their absolute stereostructures were elucidated.     

Different Lubricating Oil Treatments for the Determination of Cu,Cr, Fe,Ni, Sb,Pb, and Zn by HR-CS FAAS

Abstract

Microwave-assisted acid decomposition, direct dilution in kerosene, and oil-in-water emulsion were evaluated as lubricating oil pretreatment procedures for Cu, Cr, Fe, Ni, Pb, Sb, and Zn determination by High-Resolution Continuum Source Flame Atomic Absorption Spectrometry (HR-CS FAAS). For wet digestion, results were compared with those obtained by Flame Atomic Absorption Spectrometry (FAAS). The ultrasound probe used in emulsions sonication contaminated samples with Cr, although better results have been observed for the other six elements in this condition. In general, recovery percentages ranging from 81–106% (Cu), 80–107% (Cr), 85–114% (Fe), 82–116% (Ni), 86–117% (Pb), 85–115% (Sb), and 81–114% (Zn) were obtained. The HR-CS FAAS showed to be faster and more sensitive than FAAS.     

Homobimetallic Ruthenium-Ethylene,Vinylidene, Allenylidene,and Indenylidene Catalysts for Olefin Metathesis

Summary: Following the discovery of bimetallic ruthenium scaffold ( 1 ), two new homobimetallic ruthenium-N-heterocyclic carbene complexes ( 2 , 3 ) were synthesized and found highly suitable for promoting ROMP, RCM, and CM reactions. Results from this study indicated that the ethylene ligand was highly labile and that adding a small amount of a terminal alkyne to the reaction media had a beneficial influence on the metathetical activity. These observations prompted us to further investigate the role of the alkyne co-catalyst. Thus, homobimetallic ruthenium-arene complexes bearing vinylidene ( 4 , 5 ), allenylidene ( 6 ), and indenylidene ( 7 ) ligands were prepared from complex 1 and propargyl alcohol derivatives. Their catalytic activities were probed in several types of olefin metathesis reactions, and they were found valuable intermediates for the safe and efficient one-pot synthesis of the Hoveya–Grubbs isopropoxybenzylidene catalyst ( 8 ).     

Four new compounds, ficusal, ficusesquilignan A, B, and ficusolide diacetate from the heartwood of Ficus microcarpa

Three new lignans, ficusal (1) and ficusesquilignans A (2), B (3) and one new gamma-lactone, ficusolide diacetate (4), were isolated from the wood of Ficus microcarpa L.f. Their structures were determined by spectral evidence.     

Determination of abamectin, doramectin, emamectin, eprinomectin, ivermectin, and moxidectin in milk by liquid chromatography electrospray tandem mass specrometry

The avermectin and milbemycin families of compounds are derived from naturally occurring yeasts. They have proven to be potent preventatives against a variety of pests such as insects and parasites. Only eprinomectin and moxidectin are currently approved for use on lactating cattle with tolerances in milk of 12 microg/kg for eprinomectin and 40 microg/kg for moxidectin. Detection of misuse or inadvertent contamination in milk requires a sensitive and definitive analytical method. A method has been developed for the determination of 5 avermectins and 1 milbemycin in milk using a simple liquid-liquid extraction and liquid chromatography/tandem mass spectrometry (LC/MS/MS) analysis. Ivermectin (IVR), doramectin (DOR), abamectin (ABA), eprinomectin (EPR), emamectin (EMA), and moxidectin (MOX) were extracted from whole milk by partitioning into acetonitrile with a subsequent solvent exchange into methanol-water. Simultaneous confirmation and quantification were achieved with LC separation, positive electrospray ionization (ESI+), and MS/MS. The limits of detection ranged from 16 pg/g (ppt) for EMA to 1.7 microg/g (ppb) for MOX.     

电感耦合等离子体质谱法测定地龙药材中铅、砷、汞、镉、铜元素的残留量

建立电感耦合等离子体质谱法(ICP-MS)测定不同产地和批次地龙药材中铅(Pb)、砷(As)、汞(Hg)、镉(Cd)、铜(Cu)5种重金属元素的含量.采用微波消解进行样品前处理,结果表明:5种重金属元素的线性关系良好(r≥0.999 6),平均回收率在92.8%~95.2%范围内,方法的检出限在0.001 0~0.092 mg/kg范围内.方法灵敏度高,重复性好,方法准确.不同产地和批次的样品中5种重金属元素均有检出.地龙药材中Pb、As、Hg、Cd、Cu这5种重金属元素需要重点监控.     

Nigellamines A3, A4, A5, and C, new dolabellane-type diterpene alkaloids, with lipid metabolism-promoting activities from the Egyptian medicinal food black cumin

New dolabellane-type diterpene alkaloids, nigellamines A(3), A(4), A(5), and C, were isolated from the methanolic extract of an Egyptian medicinal food, black cumin (the seeds of Nigella sativa). Their absolute configurations were determined on the basis of chemical and physicochemical evidence. Nigellamines were found to lower triglyceride levels in primary cultured mouse hepatocytes, and in particular, the activity of nigellamine A(5) was equivalent to that of the hypolipidemic agent, clofibrate.     

SOME METAL COMPLEXES OF α, β, γ, δ-TETRA-(4-PYRIDYL) PORPHINE

Abstract

The zinc (II), copper (II), nickel (II), cobalt (II), chloromanganese (III), and chloroiron (III) complexes of α, β, γ, δ-tetra-(4-pyridyl)-porphine (4-TPyP) were prepared. The magnetic susceptibilities from near 0° to 90° K and at room temperature were measured for solid Cu(4-TPyp), Ni(4-TPyP), Co-(4-TPyP), ClMn(4-TPyP) · H₂ O and ClFe(4-TPyP). The Mössbauer spectra of ClFe(4-TPyP) were obtained at several temperatures. The infrared spectra and d-spacings were obtained for all of the solids. Electronic spectra of the complexes in pyridine and, where possible, in 0.1 N HCl solution were recorded. Evidence of intermolecular interaction was found for Co(4-TPyP), Ni(4-TPyP), and ClFe(4-TPyP).