Is vanadium a more versatile target in the activity of primordial life forms than hitherto anticipated?

The two predominant forms of vanadium occurring in the geo-, aqua- and biosphere, soluble vanadate(V) and insoluble oxovanadium(IV) (vanadyl), are subject to bacterial activity and transformation. Bacteria belonging to genera such as Shewanella, Pseudomonas and Geobacter can use vanadate as a primary electron acceptor in dissimilation or respiration, an important issue in the context of biomineralisation and soil detoxification. Azotobacter, which can employ vanadium as an essential element in nitrogen fixation, secretes a vanadophore which enables the uptake of vanadium(V). Siderophores secreted by other bacteria competitively (to ferric iron) take up vanadyl and thus interfere with iron supply, resulting in bacteriostasis. The halo-alkaliphilic Thioalkalivibrio nitratireducens possibly uses vanadium as a constituent of an alternative, molybdopterin-free nitrate reductase. Marine macro-algae can generate a variety of halogenated organic compounds by use of vanadate-dependent haloperoxidases, and a molecular vanadium compound, amavadin, from Amanita mushrooms has turned out to be an efficient catalyst in oxidation reactions. The present account is a focused and critical review of the current knowledge of the interplay of bacteria and other primitive forms of life (cyanobacteria, algae, fungi and lichens) with vanadium, with the aim to provide perspectives for applications and further investigations.     

Polonium 210Po activities in human blood of patients with ischaemic heart disease from Gdańsk in Poland

The determination of polonium ²¹⁰Po in human blood samples is presented and discussed in this paper. The human blood samples were collected from patients of Medical University of Gdańsk with ischaemic heart disease (morbus ischaemicus cordis, MIC). The polonium concentrations in analyzed human blood samples are very differentiated. ²¹⁰Po is of particular interest in public health and although is present in the environment in extremely low amounts, it is easily bioaccumulated to the human body. The study shows that the amount of ²¹⁰Po that is incorporated into the human body depends on the food habits and some difference in its levels could be observed between smokers and non-smokers.     

Distribution of Cd and Pb in a wetland ecosystem

Cadmium and lead contents in sediments, dominant species of plants (Phargmites aus-tralis and Scripus mariquter), benthos (Helice tridens tientsinensis, llyoplax deschampsi, and Bul-lacta exarata), and waders (Calidris ruficollis) on the Eastern End of Chongming Island were measured. The results showed that, for cadmium, there are clear stratification in the sediment of reclaimed area and bio-amplification in food chain. However, for lead, a phenomenon was different. The amplification factors (AFs) for cadmium of primary producers, primary consumers, and secondary consumers were 2.59-12.38, 0.09-8.44, and 51.1, respectively. For lead, AFs of primary producers, primary consumers and the top trophic layer were 0.29-2.62, 0.06-5.62, and 7.31, respectively. Each species of macrobenthos showed different strategies to cadmium and lead. Large-sized crabs accumulated more lead, while small-sized crabs and snails accumulated more cadmium. Waders had significantly highest AFs for cadmium and lead in the study. Tha     

Validation of a multi-analyte LC–MS/MS method for screening and quantification of 87 psychoactive drugs and their metabolites in hair

A multi-analyte method for the detection and quantification of 87 psychoactive drugs (antidepressants, antipsychotics, benzodiazepines, and z-drugs) in human hair has been developed and fully validated using the liquid chromatography–tandem mass spectrometry system. Due to the remarkable increase in requests of hair sample tests (such as for driver’s license renewals, child custody, DFA cases, and postmortem toxicology), we focused on the development of a rapid sample preparation. About 20 mg of hair samples, previously washed and cut into snippets, was ultrasonicated with 700 μl of methanol. Samples were then directly analyzed using a 4000 QTRAP (AB SCIEX, Foster City, CA, USA) with an electrospray ionization (ESI) Turbo V^TM Ion Source. The validation criteria parameters were satisfactory and in accordance with the international guidelines. All the compounds tested were successfully detected. One important aspect is the LODs in the low picogram per milligram concentration which may suggest a potential use of this method in cases of detection of single drug exposure. However, the LC–MS/MS method has been successfully applied for the analysis of postmortem cases (n?=?9).     

Application of a simple and sensitive GC–MS method for determination of morphine in the hair of opium abusers

Thirty hair samples were collected from male opioid abusers for whom the presence of morphine in their urine samples was confirmed by thin layer chromatography (TLC). The hair samples were decontaminated by washing with isopropanol, deionized water, and isopropanol, dried at room temperature, and cut into small pieces. Samples of the latter (30 mg ) were digested by incubation in a mixture of methanol–trifluoroacetic acid (9:1) for 18 h at 45 °C and sonicated to improve the extraction process. The methanolic phase was evaporated to dryness under a stream of nitrogen at 50 °C. The sample was derivatized by addition of N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA) and 1% trimethyliodosilane (TMIS) at 70 °C for 20 min, with sonication. Derivatized samples (1 L) were injected into a gas chromatograph–mass spectrometer (GC–MS) system fitted with a capillary column; the Finnigan MS was operated in SIM mode. Naltrexone was used as internal standard (IS). The masses of the ions selected for morphine and naltrexone were 429 and 557, respectively. The limit of quantitation was set at 0.03 ng mg^–1 hair. By using the above procedure we detected morphine in all the samples examined, in the concentration range 0.26–10.31 ng mg^–1 hair.     

Is there a carboxylic group in the sodium channel of excitable biomembranes?

A model describing the effects of H⁺, Ca²⁺ and Cd²⁺ ions on the sodium channels of excitable membranes was developed. On the basis of this model, it was shown that the decrease in the amplitude of the sodium current in the membrane of the neurones of the mollusc Helix pomatia caused by extracellular Cd²⁺, Ca²⁺ and H⁺ ions is related to the change in the near-membrane concentration of sodium ions due to a decrease of the outer surface membrane potential. The data obtained allow us to suggest that the sodium channel, contrary to the calcium channel, does not contain the carboxylic group in its selectivity filter.     

Quinolines in clothing textiles—a source of human exposure and wastewater pollution?

A production process in which the use of various types of chemicals seems to be ubiquitous makes the textile industry a growing problem regarding both public health as well as the environment. Among several substances used at each stage, the present study focuses on the quinolines, a class of compounds involved in the manufacture of dyes, some of which are skin irritants and/or classified as probable human carcinogens. A method was developed for the determination of quinoline derivatives in textile materials comprising ultrasound-assisted solvent extraction, solid phase extraction cleanup, and final analysis by gas chromatography/mass spectrometry. Quinoline and ten quinoline derivatives were determined in 31 textile samples. The clothing samples, diverse in color, material, brand, country of manufacture, and price, and intended for a broad market, were purchased from different shops in Stockholm, Sweden. Quinoline, a possible human carcinogen, was found to be the most abundant compound present in almost all of the samples investigated, reaching a level of 1.9 mg in a single garment, and it was found that quinoline and its derivatives were mainly correlated to polyester material. This study points out the importance of screening textiles with nontarget analysis to investigate the presence of chemicals in an unbiased manner. Focus should be primarily on clothing worn close to the body.     

Synthesis of platinum complexes containing (+)-bornyl- and (−)-menthylammonium in the outer coordination sphere and their catalytic activity in hydrosilylation reactions

Optically active (+)-bornyl- and (−)-menthylammonium platinates were synthesized starting from H₂[PtCl₆] · 4H₂O and hydrochlorides of the corresponding amines. Catalytic activity of the complexes in the hydrosilylation reactions of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane with 1,1,3,3-tetramethyldisiloxane and acetophenone with diphenylsilane was studied. The addition of the siloxanes leads to a predominant formation of β-adduct. Activity of the catalysts, evaluated on the 50% conversion of the substrate, decreases in the following sequence: (−)-(menthylNH₃)₂[PtCl₆] > (Et₃NH)₂[PtCl₆] > (+)-(bornylNH₃)₂[PtCl₄] > (+)-(bornylNH₃)₂[PtCl₆]. Asymmetric induction is observed in the hydrosilylation of aceto-phenone in the presence of (+)-(bornylNH₃)₂[PtCl _n ] (n = 4, 6); (+)-(bornylNH₃)₂[PtCl₆] showed the highest catalytic activity and selectivity. The hydrosilylation of acetophenone gave 1-phenylethoxy(diphenyl)silane, 1-phenylvinyloxy(diphenyl)silane, and 2-phenylethyl-2-diphenylsiloxy(diphenyl)silane as the products. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 341–349, February, 2008.     

Is a major breakthrough in the oxygen electrocatalysis possible?

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Phase composition of Mg—Al mixed oxides,their activity and selectivity in the ethanol condensation reaction

Layered hydroxides with a molar ratio of metals Mg: Al: M = 3: 1: 1 (M = Fe, Ce, Zr, Cr) were prepared and served as a basis to obtain the mixed oxides MgAlO_x, MgAlCrO_x, MgAlCeO_x, MgAlZrO_x, and MgAlCrO_x. Powder X-ray diffraction was used to study the phase composition of the oxides. It was suggested that the catalyst active surface is related to the presence of spineltype X-ray amorphous compounds. Ammonia adsorption was used to determine the total acidity, and deuterated acetonitrile adsorption was applied to estimate the strength of acid sites. The catalytic properties of complex oxides were studied in the ethanol condensation reaction. An attempt was made to correlate the catalyst activity and selectivity and the distribution of acid and base sites on the catalyst surface.     

Studies of the atomization mechanism in a graphite furnace—I. The contents of the gaseous impurities in the furnace and their variations

Using theoretical calculations of the partial pressures of gaseous impurities in the atmosphere in a GFA as a basis, the authors arrived at conclusions which are at variance with those of L'vov and frech and their co-workers. Accordingly, the partial pressure of free oxygen (p_o) in a GFA originates predominantly from the thermal decomposition of the oxides of the analyte and impurities in the matrix during atomization when the temperature is higher than 1000°C; then, p_o depends on the nature of the sample. The total amount of oxygen in a GFA depends on the initial amount of it in the argon gas and the amount released from the sample when the temperature is lower than 1000°C.The variation of the partial pressure of CO is for the first time characterized as follows: the content of CO, which is mainly dependent on the sample and the total amounts of gaseous impurities in the argon purge gas, does not vary markedly with the temperature and other factors during the whole process of atomization. The gaseous impurities exist mainly in the form of CO.     

Further study on the synthesis of F-containing porphyrins and their catalytic activity on oxidation of cyclohexene

Reaction of tetrakis(p-allyloxyphenyl)porphyrin and perfluoroalkanesulfonyl bromides givestetrakis(p-polyfluoroalkoxylphenyl)substituted porphyrins.The yields are over 90%.The synthesis ofthe metal ion complexes of these F-containing porphyrins is also reported.Preliminary results on thestudy of the catalytic activity of the manganese(Ⅲ)complexes of various fluorinated porphyrins onoxidation of cyclohexene indicate that the introduction of R_F group into porphyrin contributes to thestability of the catalysts.     

“Green synthesis” of benzothiazepine library of indeno analogues and their in vitro antimicrobial activity

A novel series of indeno-benzothiazepine derivatives was synthesised via a “green” route. Synthesis of these compounds involves the treatment of dinucleophiles such as 2-aminobenzenethiols with α,β-unsaturated ketones in poly(oxyethylene) (poly(ethylene glycol), PEG-400) catalysed by acetic acid. The synthone α,β-unsaturated ketones were obtained by Claisen-Schmidt condensation of indan-1-one with substituted pyrazole-2-carbaldehydes prompted by bleaching earth (pH 12.5) as catalyst and PEG-400 as “green” reaction solvent. Screening of all the synthesised compounds for antimicrobial activity revealed that most of these compounds exhibited moderate to significant antimicrobial activity.     

Is anthracene cofactor or spectator for the thermolysis of anthracenyl acylnitroso cycloadducts in the presence of a diene?

Acylnitroso species are very reactive dienophiles broadly used in organic synthesis. They are traditionally prepared from the oxidation of hydroxamic acids at low temperature. When this strategy fails, acylnitroso compounds may be generated from other stable sources, for example, their (9,10-dimethyl)anthracenyl cycloadducts. The thermolysis of such compounds performed in the presence of a diene leads generally to the corresponding hetero Diels-Alder (HD-A) cycloadduct in high yield with concomitant release of anthracene. The most widely accepted mechanism is the postulated slow release of acylnitroso via a retro Diels-Alder process, although the anthracenyl acylnitroso cycloadducts bear intrinsic structural features suggesting another pathway, that is, an exchange process. By using computational chemistry, we have hereby clarified the exact role of anthracene in this reaction.