Complex palytoxin‐like profile of Ostreopsis ovata. Identification of four new ovatoxins by high‐resolution liquid chromatography/mass spectrometry

Over the past decades, Italian coastlines have been plagued by recurring presence of the benthic dinoflagellate Ostreopsis ovata. Such an alga has caused severe sanitary emergencies and economic losses due to its production of palytoxin‐like compounds. Previous studies have confirmed the presence of ovatoxin‐a (OVTX‐a) as the major toxin of the algal toxin profile together with small amounts of putative palytoxin (PLTX). In our ongoing research on O. ovata toxins we report herein on in‐depth investigation of an O. ovata culture carried out by high‐resolution (HR) liquid chromatography/mass spectrometry (LC/MS) and tandem mass spectrometry (MS²). Particularly, the presence of putative PLTX and OVTX‐a was confirmed and the occurrence in the extract of four new palytoxin‐like compounds, OVTX‐b, ‐c, ‐d, and ‐e, was highlighted. Elemental formulae have been assigned to the new ovatoxins and information has been gained about their structural features. A quantitative study of the O. ovata culture extract indicated that the whole of the new ovatoxins represents about 46% of the total toxin content and, thus, their presence has to be taken into account when LC/MS‐based monitoring programs of either plankton or contaminated seafood are carried out. Copyright © 2010 John Wiley & Sons, Ltd.     

Mass spectrometry of some dichloroacetamides of pharmacological interest. Evidence for an unusual skeletal rearrangement

The mass spectrometric behaviour of six N-(2-ethoxyethyl)-N-p-substituted benzyldichloroacetamides is described and discussed in detail with the aid of exact mass measurements, metastable analysis and mass-analysed ion kinetic energy spectrometry. The presence of an unusual skeletal rearrangement is described.     

Structural study of alkaloids from securidaca longipedunculata roots. II. Isolation and characterization by supercritical fluid chromatography/mass spectrometry

Various alkaloids obtained from the methanol extracts of the roots of Securidaca Longipedunculata Fres. were studied using supercritical fluid chromatography/mass spectrometry. This hyphenated method and parallel unimolecular and collisionally activated decomposition experiments on electron impact-generated molecular ions gave information on the structure of compounds. The presence of the ergoline skeleton in some of them was assigned.     

Hydrazines et hydrazones heterocycliques. III. Synthese de derives du naphto[2,3-d]thiazole

The synthesis of 2-hydrazinonaphtho[2,3-d]thiazole, 3-methylnaphtho-[2,3-d]thiazolin-2-one hydrazone and some of the corresponding 2-alkylidenehydrazino-3-methylnaphtho[2,3-d]thiazoles is described. These compounds have been characterized by their infrared, ultraviolet, nmr spectra in the presence of Eu(fod)₃ and by their mass spectra.     

Mass spectrometry in the study of extracellular enzymes produced by filamentous fungi

The use of MALDI-TOF and other types of mass spectrometry for the identification and investigation of extracellular enzymes (carbohydrases, proteinases, esterases, etc.) produced by filamentous fungi belonging to the genera Aspergillus, Trichoderma, Penicilium, Chrysosporium, etc. is discussed. The method of mass spectrometric peptide fingerprinting combined with the use of Internet software for on line data analysis (MASCOT, Aldente, FindPept, FindMod, GlycoMod) allows the fast and reliable identification of both individual enzymes and the components of crude multienzyme preparations without their fractionation. The method was also applied to the discrimination of the fungal genes encoding enzymes with similar substrate specificity. Other enzyme-based applications of mass spectrometry, such as the revelation of the presence or absence of structural domains in the molecules of carbohydrases, the detection of posttranslational and artificial modifications in the enzymes, and the use of tandem mass spectrometry for de novo peptide sequencing are described.     

Ringschlüsse an Chinonylmethanfarbstoffen und analogen Merocyaninen. 4. Mitteilung. Dihydro-anthracenophenazinone

Dihydro-anthracenophenazinones (Cyclization of Quinonylmethane Dyes), 4th Communication. Substituted dihydroanthraceno[1,2-b]phenazinones were synthetized by reaction of 1-alkyl-2,3-dimethyl-quinoxalinium-perchlorates with dichloro- or tetrachloro-1,4-anthraquinone and cyclization of the intermediate quinoxalylidenmethyl-1, 4-anthraquinones. The tetrachloro derivative of 1,4-anthraquinone obtained by chlorination in boiling acetic acid in the presence of iodine is identified to be the 2,3,6,9-isomer. The properties of the dihydroanthraceno[1,2-b]phenazinones are discussed. The visible, mass, and some ¹H-NMR. spectra are given.     

Direct detection of nanoparticles and components in smoke by time-of-flight mass spectrometry with soft plasma ionization

A new system combining a soft plasma ionization (SPI) source with a time-of-flight mass spectrometer (TOFMS) has been successfully developed and applied to direct and on-line analysis of nanoparticles in smoke generated during combustion of mosquito coils with no sample preparation. The mass spectra of nanoparticles in smoke were examined in conjunction with the effects of species, pressure and current of the SPI discharge on fragmentation. The results indicated that a maximum mass of m/z 1576 was detectable when the following optima SPI conditions were satisfied: a He gas pressure of 1000 Pa with an air pressure of 1600 Pa and a discharge current of 110 mA. Furthermore, considering the results for emission spectra we suppose an ionization mechanism of SPI in which excitation and ionization of nitrogen molecule is promoted by the presence of He gas, leading to promote the smoke sample ionization. The mass spectrum of nanoparticles showed specific patterns of a peak interval of 74 which were assigned to triacetylene (1,3,5-hexatriyne). The most abundant peak in the mass spectrum, at m/z 452, was assigned to triacontanoic acid.     

Studies on phenothiazines. Part 7. Synthesis of 3-substituted 2-aminobenzenethiols and their conversion into phenothiazines

Synthesis of substituted 1-nitrophenothiazines is reported by the Smiles rearrangement in situ, which involves condensation of 3-chloro or methyl-2-aminobenzenethiol with o-halonitrobenzenes (2,4,6-trinitochloro-benzene, 1,4-dichloro-2,6-dinitrobenzene, 2,4,6-tribromo-1,3-dinitrobenzene) in the presence of ethanolic sodium hydroxide. Ir and mass spectral studies are included.     

Mass transfer and fluid flow visualization in packed and fluidized beds by the adsorption method

Mass transfer coefficient (j _D ) between fluid and column wall in liquid packed and fluidized beds of spherical inert particle has been studied experimentally using adsorption method. Experiments were conducted in column 40 mm in diameter for packed and fluidized beds. In all runs mass transfer rates were determined in presence of spherical glass particles 2.06 mm in diameter. This paper introduced adsorption method as very suitable method for studies of mass transfer and for fluid flow visualization. The adsorption method is based on the dynamic adsorption of an organic dye onto a surface covered with a thin layer of a porous adsorbent. Local and average mass transfer coefficients were determinated from the surface color intensity of the foils of silica gel. Correlation j _D = f(Re) was derived using mass transfer coefficients data. The article is published in the original.     

Monitoring the Hydrolysis of p—Nitrophenyl Acetate Catalyzed by Seryl—histidine with Electrospray Ionization Mass Spectrometry

ＩｎｔｒｏｄｕｃｔｉｏｎＩｎｔｈｅｐａｓｔｄｅｃａｄｅ ,ｉｔｗａｓｆｏｕｎｄｔｈａｔｔｗｏａｍｉｎｏａｃｉｄｒｅｓｉｄｕｅｓ ,ＳｅｒａｎｄＨｉｓ ,ｗｏｒｋａｓｔｈｅａｃｔｉｖｅｓｉｔｅｓｉｎｔｈｅｓｅｒ ｉｎｅｐｒｏｔｅａｓｅ .1 3 Ｉｎｏｕｒｐｒｅｖｉｏｕｓｗｏｒｋ ,ａｄｉｐｅｐｔｉｄｅｓｅｒｙｌ ｈｉｓｔｉｄｉｎｅ (Ｓｅｒ Ｈｉｓ)ｗａｓｆｏｕｎｄｔｏｈａｖｅｔｈｅｐｒｏｔｅｉｎａｎｄｎｕ ｃｌｅｏｓｉｄｅｓｃｌｅａｖａｇｅａｃｔｉｖｉｔｙ .4 7ｐ Ｎｉｔｒｏｐｈｅｎｙｌａｃｅｔａｔｅ (ｐ ＮＰＡ)ｗ…     

Identification of polymeric procyanidins from pine bark by mass spectrometry

Pine bark is an important source of polyphenolic compounds, mainly procyanidins, with reported protective effects against disease. In previous works, barks of two varieties of pine (P. pinaster and P. radiata) were extracted with ethanol, and partially purified to obtain the aqueous fractions (FA), that contained mainly polymeric procyanidins. The mean degree of polymerization was 7.9 for radiata (rFA) and 10.6 for pinaster (pFA). FAs were chromatographed on Sephadex LH‐20 by using a gradient of methanol, water and acetone, to render a series of sub‐fractions. In this work, the procyanidin compositions of these sub‐fractions were analyzed using matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS). The mass spectra of sub‐fractions from FA of P. pinaster showed signals of procyanidin polymers up to tridecamers, whereas for those from P. radiata the maximum degree of polymerization was 15. For this latter case, the MALDI‐TOF mass spectra detected the presence of prodelphinidins in a small amount. Copyright © 2009 John Wiley & Sons, Ltd.     

P450‐catalyzed vs. electrochemical oxidation of haloperidol studied by ultra‐performance liquid chromatography/electrospray ionization mass spectrometry

The metabolites formed via the major metabolic pathways of haloperidol in liver microsomes, N‐dealkylation and ring oxidation to the pyridinium species, were produced by electrochemical oxidation and characterized by ultra‐performance liquid chromatography/electrospray ionization mass spectrometry (UPLC/ESI‐MS). Liver microsomal incubations and electrochemical oxidation in the presence of potassium cyanide (KCN) resulted in two diastereomeric cyano adducts, proposed to be generated from trapping of the endocyclic iminium species of haloperidol. Electrochemical oxidation of haloperidol in the presence of KCN gave a third isomeric cyano adduct, resulting from trapping of the exocyclic iminium species of haloperidol. In the electrochemical experiments, addition of KCN almost completely blocked the formation of the major oxidation products, namely the N‐dealkylated products, the pyridinium species and a putative lactam. This major shift in product formation by electrochemical oxidation was not observed for the liver microsomal incubations where the N‐dealkylation and the pyridinium species were the major metabolites also in the presence of KCN. The previously not observed dihydropyridinium species of haloperidol was detected in the samples, both from electrochemical oxidation and the liver microsomal incubations, in the presence of KCN. The presence of the dihydropyridinium species and the absence of the corresponding cyano adduct lead to the speculation that an unstable cyano adduct was formed, but that cyanide was eliminated to regenerate the stable conjugated system. The formation of the exocyclic cyano adduct in the electrochemical experiments but not in the liver microsomal incubations suggests that the exocyclic iminium intermediate, obligatory in the electrochemically mediated N‐dealkylation, may not be formed in the P450‐catalyzed reaction. Copyright © 2010 John Wiley & Sons, Ltd.     

Laser desorption/ionization fourier transform mass spectrometry of thin films deposited on silicon by plasma polymerization of acetylene

Thin films deposited on silicon substrate by three different methods of plasma polymerization of acetylene were analyzed by direct laser desorption/ionization Fourier transform mass spectrometry. High-resolution mass spectra showed the presence of carbon clusters and hydrocarbon oligomers in different relative abundances. During unipolar and continuous discharge polymerization of acetylene-hydrogen gas mixtures, quadrupole mass spectra of the plasma constituents showed the presence of molecular species with m/z lower than 100 — mainly peaks of C₄H₂ and C₆H₂. Films produced had smooth surfaces and the corresponding LDI-FTMS spectra displayed only carbon cluster signals in the positive ion mode and both hydrocarbon and carbon cluster signals (with much higher relative abundance of carbon cluster signals) in the negative ion mode. Alternatively, during bipolar discharge with either higher acetylene gas flux (>40 cm³/min) or longer deposition times (>10 min), quadrupole mass spectra of the plasma constituents showed signals corresponding to polycyclic aromatic hydrocarbons (PAH) with m/z higher than 100. SEM pictures of the bipolar thin films demonstrated the presence of “flower” structures and nanoparticles developed on the surface. LDI-FTMS spectra of such thin films showed either total absence or lower relative abundance of carbon cluster signals, compared with hydrocarbon signals.     

Stereochemical effects in mass spectrometry. 7. Determination of absolute configuration of some organic molecules by reaction mass spectrometry

It was found that in the chemical ionization (isobutane) mass spectra of some asymmetric secondary alcohols and α-amino acids, when a pair of enantiomers (such as R- and S-2-phenyIbutyric anhydride, R- and S-mandelic acid, R- and S-2-methylbutanoic acid or R- and S-α-phenyl ethyl amine) were used as reaction reagents, the relative abundances of characteristic ions formed by the stereoselective reaction between sample and reagent of the same configuration were much higher than those ions formed by the sample and a reagent of a different configuration. The absolute configuration of the sample molecule may be predicted by examination of mass spectra of the sample measured with R- and S-reagent respectively. This approach proved to be a convenient way for determination of the absolute configurations of organic molecules on a micromole level by mass Spectrometry.     

Characterization of blocked nucleosides by mass spectrometry. Benzyl derivatives

The mass spectra of eleven model monobenzylated nucleosides were studied using low and high resolution mass spectrometry. Structural assignments to the major ions were made and several decomposition mechanisms proposed, with the goal of establishing the uses and limitations of mass spectrometry for the characterization of benzylaled nucleosides. Mass spectra generally permit determination of the extent and site of benzylation, with particular regard to base vs. sugar substitution, 0–2′ vs. 0–3′ or 0–5′, and in some cases 0–5′ vs. other isomers.     

The effects of selected phytochemicals on biofilm formed by five methicillin-resistant Staphylococcus aureus

The aim of this study was to evaluate the ability of 0.1% thyme oil (TO), trans-cinnamaldehyde (TC), ferulic acid (FA), p-coumaric acid (p-CA), caffeic acid (CA), lavender essential oil (LO), geranium essential oil (GO) and tee tree oil (TTO) to control biofilms formed by methicillin-resistant Staphylococcus aureus (MRSA) strains. Depending on the strains, TO reduced 59.7–85% of biofilm mass, while TC 52.9–82.4% after 48 h of treatment. Reduction of metabolic activity of biofilms in ranges 79.3–86% and 85.9–88.7% was observed after 48 h of TC and TO of treatment, respectively. In the case of some strains, reduction of biofilm mass in the presence of FA, CA, GO, LO and TTO was not observed. This study showed that TO and TC might have therapeutic potential as an inhibitory agents for use in MRSA biofilm-related infections.     

Determination of Rosiglitazone by Direct Analysis in Real-Time Mass Spectrometry

The determination of rosiglitazone in dietary supplements by direct analysis in real-time mass spectrometry normally provides low repeatability. The [M+H]⁺ signal sharply decreased in the presence of strong-base and weak-acid ionic compounds because rosiglitazone decomposition occurred due to the hydrolysis of strong-base and weak-acid anions. The repeatability was improved and the influence of ionic compounds was minimized by the use of pioglitazone as an internal standard. Orbitrap mass spectrometry was used to provide high resolution in which isotopic interferences from M?+?1 of pioglitazone upon M of rosiglitazone were eliminated. This approach was used to determine rosiglitazone in tablet and dietary supplements in 1?min per sample.     

Discovery of bound and unbound waters in crystalline amino acids revealed by thermal analysis

The thermal analytical study of most hydrophobic and hydrophilic D/L amino acids reveals significant hydropathy index correlation between the presence of water and crystalline amino acids. The TG derivative mass profiles for arginine and lysine (hydrophilic acids) at various time intervals of atmospheric exposure, show two distinct peaks, one between 50 and 60°C (unbound water), and one close to 100°C (bound-like water). The DSC heat-cool profiles for lysine and arginine confirmed the presence of these multiple waters with two heats of vaporization. The absence of these patterns from the TG and DSC for cysteine and phenylalanine (hydrophobic acids) further supports the conclusions.     

Reaction of aminoalcohols with butadiene catalyzed by palladium complexes. Preliminary communication

The aminoalcohols 1 , react with 2 equivalents of butadiene in the presence of catalytic quantities of bis (acetylacetonato)palladium/triphenylphosphine to give exclusively the corresponding N-octadienyl amninoalcohols. In the presence of excess butadiene, subsequent O-octadienylation occurs only for N-octadienylimino-diethanol 2g , affording the monoether 4g . O-octadienylation of 2a-f and 4g can be effected by the addition of molar quantities of triethylamine to the reaction mixture.     

Phytoecdysones ofAjuga turkestanica VI. 22-Acetylcyasterone

Summary The leaves ofAjuga turkestanica (Rg1.) Briq. have yielded a new ecdysone — 22-acetyl-cyasterone. The mass spectrum of this new ecdysone and the features of it due to the presence of the acetoxy group at C-22 have been discussed.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 215–219, March–April, 1978.