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91.
Analysis of nitromethane from samples exposed in vitro to chloropicrin by stable isotope dilution headspace gas chromatography with mass spectrometry 下载免费PDF全文
Mia Halme Maija Pesonen Toni Grandell Matti Kuula Markku Pasanen Kirsi Vähäkangas Paula Vanninen 《Journal of separation science》2015,38(19):3383-3389
Chloropicrin (trichloronitromethane) is a widely used soil fumigant and an old chemical warfare agent. The metabolism of chloropicrin is not well known in mammals but nitromethane has been shown to be one of its main metabolites. Here, a fast and simple headspace gas chromatography with mass spectrometry method was applied for the measurement of nitromethane from aqueous samples. The analytical method was validated using stable isotope labeled internal standard and a small sample volume of 260 μL. No conventional sample preparation steps were needed. The method was accurate (relative standard deviations ≤1.5%) and linear (R2 = 0.9996) within the concentration range of 0.1?6.0 μg/mL. This method was used to measure nitromethane in in vitro incubations with human and pig liver cell fractions containing enzymes for xenobiotic metabolism, exposed to chloropicrin. The results indicate that the presence of glutathione is necessary for the formation of nitromethane from chloropicrin. Also, nitromethane was formed mostly in liver cytosol fractions, but not in microsomal fractions after the incubation with chloropicrin. Our results suggest that although nitromethane is not the unequivocal biomarker of chloropicrin exposure, this method could be applied for screening the elevated levels in humans after chloropicrin exposure. 相似文献
92.
Münzel M Lischke U Stathis D Pfaffeneder T Gnerlich FA Deiml CA Koch SC Karaghiosoff K Carell T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(49):13782-13788
5-Formylcytosine (fC or (5-CHO)dC) and 5-carboxylcytosine (caC or (5-COOH)dC) have recently been identified as constituents of mammalian DNA. The nucleosides are formed from 5-methylcytosine (mC or (5-Me)dC) via 5-hydroxymethylcytosine (hmC or (5-HOMe)dC) and are possible intermediates of an active DNA demethylation process. Here we show efficient syntheses of phosphoramidites which enable the synthesis of DNA strands containing these cytosine modifications based on Pd(0)-catalyzed functionalization of 5-iododeoxycytidine. The first crystal structure of fC reveals the existence of an intramolecular H-bond between the exocyclic amine and the formyl group, which controls the conformation of the formyl substituent. Using a newly designed in vitro mutagenicity assay we show that fC and caC are only marginally mutagenic, which is a prerequisite for the bases to function as epigenetic control units. 相似文献
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94.
Cells continuously produce reactive oxidative species that can modify all cellular components. In proteins, for example, cysteine, methionine, tryptophan (Trp), and tyrosine residues are particularly prone to oxidation. Here, we report two new approaches to distinguish two isomeric oxidation products of Trp residues, i.e. 5-hydroxytryptophan (5-HTP) and oxindolylalanine (Oia) residues, in peptides. First, 2-nitrobenzenesulfenyl chloride, known to derivatize Trp residues in position 2 of the indole ring, was used to label 5-HTP residues. The mass shift of 152.98 m/z units allowed identifying 5-HTP- besides Trp-containing peptides by mass spectrometry, whereas Oia residues were not labeled. Second, fragmentation of the Oia- and 5-HTP-derived immonium ions at m/z 175.08 produced ions characteristic for each residue that allowed their identification even in the presence of y(1) ions at m/z 175.12 derived from peptides with C-terminal arginine residues. The pseudo MS(3) spectra acquired on a quadrupole time-of-flight hybrid mass spectrometer displayed two signals at m/z 130.05 and m/z 132.05 characteristic for Oia-containing peptides and a group of six signals (m/z 103.04, 120.04, 130.04, 133.03, 146.04, and 148.04) for 5-HTP-cointaining peptides. In both cases, the relative signal intensities appeared to be independent of the sequence providing a specific fingerprint of each oxidative modification. 相似文献
95.
96.
JPC – Journal of Planar Chromatography – Modern TLC - Prostaglandins are biological lipid mediators that control a variety of physiological and pathophysiological processes. They... 相似文献
97.
Johannes Kiefer Franziska Toni Karl‐Ernst Wirth 《Journal of Raman spectroscopy : JRS》2015,46(11):1124-1128
Raman spectroscopy is applied to study the interactions between carbon‐coated iron nanoparticles and ethanol. The spectra reveal changes in the vibrational structure of ethanol, despite dispersion of only a very small amount of nanoparticles. The hydrogen bonding network of ethanol is significantly affected in the presence of the particles. This is revealed by frequency shifts throughout the spectrum as well as the modification of the OH stretching band of the alcohol. The carbon shell of the nanoparticles does not exhibit polar groups, and hence the non‐polar interactions in the system are strengthened and the hydrogen bonding is weakened. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
98.
Sigmatropic Rearrangement of Vinyl Aziridines: Expedient Synthesis of Cyclic Sulfoximines from Chiral Sulfinimines 下载免费PDF全文
Dr. Toni Moragas Ryan M. Liffey Dr. Dominika Regentová Jon‐Paul S. Ward Justine Dutton Dr. William Lewis Prof. Ian Churcher Dr. Lesley Walton Dr. José A. Souto Prof. Robert A. Stockman 《Angewandte Chemie (International ed. in English)》2016,55(34):10047-10051
A novel rearrangement of 2‐vinyl aziridine 2‐carboxylates to unusual chiral cyclic sulfoximines is described herein. The method allows the synthesis of substituted cyclic sulfoximines in high yields with complete stereocontrol, and tolerates a wide substrate scope. A one‐pot process starting directly from sulfinimines provides access to complex chiral sulfoximines in only two steps from commercially available aldehydes. A mechanistic hypothesis and synthetic application in the formal synthesis of trachelanthamidine, by transformation of a cyclic sulfoximine into a pyrroline, is also disclosed. 相似文献
99.
Cell suspension cultures of Lavandula angustifolia Mill. ssp. angustifolia (syn.: L. officinalis Chaix.) afforded a fatty acid composition, cis and trans p-coumaric acids (=p-hydroxy cinnamic acids), and beta-sitosterol. The fatty acid composition was analyzed by GC-MS, and the structures of the isolated three compounds were determined by 1H- and 13C-NMR, and MS spectroscopic techniques. 相似文献
100.
Toni Andersson Susanna Holappa Vladimir Aseyev Heikki Tenhu 《Journal of polymer science. Part A, Polymer chemistry》2003,41(13):1904-1914
The interactions between oppositely charged polyelectrolytes were studied in saline aqueous solutions as functions of the temperature and the salt and polymer concentrations. The polyanion was a diblock copolymer composed of a poly(ethylene oxide) block and a poly(sodium methacrylate) block. Two polycations were used, the homopolymer poly(methacryl oxyethyl trimethylammonium chloride) and its poly(ethylene oxide)‐grafted analogue. By dynamic light scattering and turbidity measurements, it was observed that the salt concentration, temperature, and counterion size had a significant effect on the formation of the polymer complexes in aqueous solutions. At a fixed salt concentration and a fixed temperature, it was possible to form completely soluble complexes of an ionic polymer in aqueous solutions between poly(ethylene oxide)‐grafted poly(methacryl oxyethyl trimethylammonium chloride)and the polyanion with a poly(ethylene oxide) block at a 1:1 anion/cation ratio. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1904–1914, 2003 相似文献