Monatshefte Fur Chemie最新文献

Abstract: Commonly known as a highly toxic chemical, cyanide is also an essential reagent for many industrial processes. It naturally occurs in plant seeds as cyanogenic glycosides. Another relatively common mode of cyanide exposure is inhalation of environmental tobacco smoke. This study concerns importance to determine cyanide ion in human biological samples. Urine and saliva samples were collected healthy volunteers exposed to tobacco smoke (active smokers) and environmental tobacco smoke (passive smokers). Chromatographic separation was achieved with an anion-exchange column and separated ions were detected by a pulsed amperometric detector. The method produced linear response in a specific concentration range of cyanide ion. The limit of detection was estimated at 0.1  and 0.5 µg/dm³ for urine and saliva samples, respectively. Cyanide ion concentrations in samples ranged from not detected (below LOD) to 12.88 µg/dm³. The comparison of results of biological samples analyses shows an increasing trend in cyanide concentration that may suggest that environmental tobacco smoke might have an impact on human health.

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Abstract: Mass methanol poisonings present a serious problem for health systems worldwide, with poor outcome associated with delayed treatment. Positive pre-hospital serum ethanol concentration may have predictive value as the prognostic factor of the treatment outcome. We studied the effect of positive serum ethanol level on admission to hospital on survival in patients treated during the Czech methanol outbreak during 2012-2014. Cross-sectional cohort study was performed in 100 hospitalized patients with confirmed methanol poisoning. Pre-hospital ethanol was administered in 42 patients (by paramedic/medical staff to 30 patients and self-administered by 12 patients before admission); 58 patients did not receive pre-hospital ethanol. Forty-two patients had detectable serum ethanol concentration on admission to hospital [median 18.3 (IQR 6.6-32.2) mmol dm^-3]. Pre-hospital ethanol administration by paramedic/medical staff had a significant effect on survival without visual and CNS sequelae when adjusted for arterial blood pH on admission (OR 8.73; 95 % CI 3.57-21.34; p < 0.001). No patients receiving pre-hospital ethanol died compared with 21 not receiving (p < 0.001). Positive serum ethanol concentration on admission to hospital was a predictor for survival without health sequelae when adjusted for arterial blood pH (OR 8.10; 95 % CI 2.85-23.02; p < 0.001). The probability of visual and CNS sequelae in survivors reduced with increasing serum ethanol concentration on admission.

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Abstract: This manuscript describes the convergent synthesis of aryl- and alkyl-disubstituted γ-pyrones from β-ketoacids. The reaction proceeds in the presence of trifluoromethanesulfonic anhydride via an unprecedented decarboxylative auto-condensation of the starting material. Herein, the scope and limitations of this transformation are reported.

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Abstract: Cytochrome P450 (CYP) 1A1 is the most important enzyme activating and detoxifying the human carcinogen benzo[a]pyrene (BaP). In the previous studies, we had shown that not only the canonic NADPH:CYP oxidoreductase (POR) can act as electron donor but also cytochrome b₅ and its reductase, NADH:cytochrome b₅ reductase. Here, we studied the role of the expression system used on the metabolites generated and the levels of DNA adducts formed by activated BaP. We used an eukaryotic and a prokaryotic cellular system (Supersomes, microsomes isolated from insect cells, and Bactosomes, a membrane fraction of Escherichia coli, each transfected with cDNA of human CYP1A1 and POR). These were reconstituted with cytochrome b₅ with and without NADH:cytochrome b₅ reductase. We evaluated the effectiveness of each cofactor, NADPH and NADH, to mediate BaP metabolism. We found that both systems differ in catalysing the reactions activating and detoxifying BaP. Two BaP-derived DNA adducts were generated by the CYP1A1-Supersomes, both in the presence of NADPH and NADH, whereas NADPH but not NADH was able to support this reaction in the CYP1A1-Bactosomes. Seven BaP metabolites were found in Supersomes with NADPH or NADH, whereas NADPH but not NADH was able to generate five BaP metabolites in Bactosomes. Our study demonstrates different catalytic efficiencies of CYP1A1 expressed in prokaryotic and eukaryotic cells in BaP bioactivation indicating some limitations in the use of E. coli cells for such studies.

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Abstract: Ellipticine is an anticancer agent that forms covalent DNA adducts after enzymatic activation by cytochrome P450 (CYP) enzymes, mainly by CYP3A4. This process is one of the most important ellipticine DNA-damaging mechanisms for its antitumor action. Here, we investigated the efficiencies of human hepatic microsomes and human recombinant CYP3A4 expressed with its reductase, NADPH:CYP oxidoreductase (POR), NADH:cytochrome b₅ reductase and/or cytochrome b₅ in Supersomes™ to oxidize this drug. We also evaluated the effectiveness of coenzymes of two of the microsomal reductases, NADPH as a coenzyme of POR, and NADH as a coenzyme of NADH:cytochrome b₅ reductase, to mediate ellipticine oxidation in these enzyme systems. Using HPLC analysis we detected up to five ellipticine metabolites, which were formed by human hepatic microsomes and human CYP3A4 in the presence of NADPH or NADH. Among ellipticine metabolites, 9-hydroxy-, 12-hydroxy-, and 13-hydroxyellipticine were formed by hepatic microsomes as the major metabolites, while 7-hydroxyellipticine and the ellipticine N²-oxide were the minor ones. Human CYP3A4 in Supersomes™ generated only three metabolic products, 9-hydroxy-, 12-hydroxy-, and 13-hydroxyellipticine. Using the ³²P-postlabeling method two ellipticine-derived DNA adducts were generated by microsomes and the CYP3A4-Supersome system, both in the presence of NADPH and NADH. These adducts were derived from the reaction of 13-hydroxy- and 12-hydroxyellipticine with deoxyguanosine in DNA. In the presence of NADPH or NADH, cytochrome b₅ stimulated the CYP3A4-mediated oxidation of ellipticine, but the stimulation effect differed for individual ellipticine metabolites. This heme protein also stimulated the formation of both ellipticine-DNA adducts. The results demonstrate that cytochrome b₅ plays a dual role in the CYP3A4-catalyzed oxidation of ellipticine: (1) cytochrome b₅ mediates CYP3A4 catalytic activities by donating the first and second electron to this enzyme in its catalytic cycle, indicating that NADH:cytochrome b₅ reductase can substitute NADPH-dependent POR in this enzymatic reaction and (2) cytochrome b₅ can act as an allosteric modifier of the CYP3A4 oxygenase.

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Abstract: The use of square wave voltammetry (SWV) and square wave adsorptive stripping voltammetry (SWAdSV) in conjunction with a cyclic renewable silver amalgam film electrode for the determination of flumetralin is presented. Poor separation of two overlapped reduction peaks is significantly improved when hexadecyltrimethylammonium bromide is used as a component of the supporting electrolyte solution (together with BR buffer pH 9.5). The SW technique parameters were investigated and found optimal as follows: frequency 50 Hz, amplitude 40 mV, and step potential 5 mV. Accumulation time and potential were studied to select the optimal conditions in adsorptive voltammetry. The analytical curve was linear for the flumetralin concentration range from 1.0 × 10^-6 to 1.0 × 10^-5 mol dm^-3 and from 5.0 × 10^-9 to 1.0 × 10^-7 mol dm^-3 for SWV and SWAdSV, respectively. Detection limit of 6.5 × 10^-10 mol dm^-3 was calculated for accumulation time 60 s at -0.2 V. The repeatability of the method was determined at a flumetralin concentration level equal to 5.0 × 10^-9 mol dm^-3 and expressed as %RSD = 5.0% (n = 6). The proposed method was applied and validated successfully by studying the recovery of herbicide content in spiked environmental samples.

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Abstract: To ensure that chicken meat products are safe to consume, it is important to be able to reliably determine its shelf-life. To assess the applicability of ultra-fast gas chromatography and electronic nose technology in evaluation of poultry, an analysis of the headspace of ground chicken meat samples refrigerated over a period of 7 days was performed. Chemometric techniques were used to mine additional information from a multiparametric data set. As a reference, sensory evaluation was also conducted, and several volatile chemical compounds that can potentially be used as poultry meat decomposition indicators were identified. The obtained results suggest the possibility of using both techniques to supplement the established methods of chicken meat quality assessment.

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Abstract: Field olfactometry is one of the sensory techniques used to determine odour concentration, in atmospheric air, directly in emission sources. A two-dimensional gas chromatography with time of flight mass spectrometer (GC×GC-TOF-MS) allows performing the chemical characterization of various groups of chemical compounds, even in complex mixtures. Application of these techniques enabled determination of odour concentration level in atmospheric air in a vicinity of the oil refinery and the neighbouring wastewater treatment plant. The atmospheric air samples were analysed during a time period extending from February to June 2016. Based on the GC×GC-TOF-MS analysis and odour threshold values, the theoretical odour concentrations were calculated and compared with the odour concentrations determined by field olfactometry technique. The investigations revealed that higher values of odour concentration were obtained with the field olfactometry technique where odour analysis was based on holistic measurement. It was observed that the measurement site or meteorological conditions had significant influence on odour concentration level. The paper also discusses the fundamental analytical instruments utilized in the analysis of odorous compounds and their mixtures.

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Abstract: The herbal drug aristolochic acid, a natural mixture of 8-methoxy-6-nitrophenanthro[3,4-d]-1,3-dioxole-5-carboxylic acid (AAI) and 6-nitrophenanthro[3,4-d]-1,3-dioxole-5-carboxylic acid (AAII), is derived from Aristolochia species and is the cause of two nephropathies. Ingestion of aristolochic acid is associated with the development of urothelial tumors linked with aristolochic acid nephropathy and is implicated in the development of Balkan endemic nephropathy-associated urothelial tumors. The O-demethylated metabolite of AAI, 8-hydroxyaristolochic acid (AAIa), is the detoxification product of AAI generated by its oxidative metabolism. Whereas the formation of AAIa from AAI by cytochrome P450 (CYP) enzymes has been found in vitro and in vivo, this metabolite has not been found from AAII as yet. Therefore, the present study has been designed to compare the amenability of AAI and AAII to oxidation; experimental and theoretical approaches were used for such a study. In the case of experimental approaches, the enzyme (CYP)-mediated formation of AAIa from both carcinogens was investigated using CYP enzymes present in subcellular microsomal fractions and recombinant CYP enzymes. We found that in contrast to AAI, AAII is oxidized only by several CYP enzymatic systems and their efficiency is much lower for oxidation of AAII than AAI. Using the theoretical approaches, such as flexible in silico docking methods and ab initio calculations, contribution to explanation of these differences was established. Indeed, the results found by both used approaches determined the reasons why AAI is better oxidized than AAII; the key factor causing the differences in AAI and AAII oxidation is their different amenability to chemical oxidation.

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Abstract: Herein, we describe the synthesis and characterization of a conjugated donor-acceptor copolymer consisting of a pyrrolopyridazinedione (PPD) acceptor unit, and a benzodithiophene (BDT) donor unit. The polymerization was done via a Stille cross-coupling polycondensation. The resulting PPD-BDT copolymer revealed an optical bandgap of 1.8 eV and good processability from chlorobenzene solutions. In an organic solar cell in combination with PC₇₀BM, the polymer led to a power conversion efficiency of 4.5%. Moreover, the performance of the copolymer was evaluated in polymer/nanocrystal hybrid solar cells using non-toxic CuInS₂ nanocrystals as inorganic phase, which were prepared from precursors directly in the polymer matrix without using additional capping ligands. The PPD-BDT/CuInS₂ hybrid solar cells showed comparably high photovoltages and a power conversion efficiency of 2.2%.

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