Analysis of phenolic choline esters from seeds of Arabidopsis thaliana and Brassica napus by capillary liquid chromatography/electrospray‐ tandem mass spectrometry

Total phenolic choline ester fractions prepared from seeds of Arabidopsis thaliana and Brassica napus were analyzed by capillary LC/ESI‐QTOF‐MS and direct infusion ESI‐FTICR‐MS. In addition to the dominating sinapoylcholine, 30 phenolic choline esters could be identified based on accurate mass measurements, interpretation of collision‐induced dissociation (CID) mass spectra, and synthesis of selected representatives. The compounds identified so far include substituted hydroxycinnamoyl‐ and hydroxybenzoylcholines, respective monohexosides as well as oxidative coupling products of phenolic choline esters and monolignols. Phenolic choline esters are well separable by reversed‐phase liquid chromatography and sensitively detectable using electrospray ionization mass spectrometry in positive ion mode. CID mass spectra obtained from molecular ions facilitate the characterization of both the type and substitution pattern of such compounds. Therefore, LC/ESI‐MS/MS represents a valuable tool for comprehensive qualitative and quantitative analysis of this compound class. Copyright © 2008 John Wiley & Sons, Ltd.     

Inflammation markers in point-of-care testing (POCT)

Inflammation is a central issue in medicine. Inflammatory processes may be local or systemic, acute or chronic, and they may be benign or fatal. In bacterial or viral infections fast and reliable diagnosis is essential for appropriate treatment, e.g. antimicrobial therapy. The time to diagnosis is critical because uncontrolled infections may lead to sepsis with a mortality rate close to 50%. Beside clinical signs, laboratory markers are important in detecting, differentiating, and monitoring inflammation, particularly acute infections. Currently several inflammation markers including leukocyte count and leukocyte differentiation, C-reactive protein (CRP), procalcitonin (PCT), and interleukins (IL) 6 and 8, is available, and potential future serum markers are under development. In this article the clinical use of these markers in routine laboratory and in point-of-care testing is described and the diagnostic value of the four groups of laboratory marker is compared. Current data show that leukocyte count or, better, neutrophil count, CRP, and PCT are well suited to support of rapid diagnosis of inflammation and infections in children and adults whereas measurement of IL-6 and 8 are preferable for detection of sepsis in neonates.     

Bifurcations in the space of exponential maps

This article investigates the parameter space of the exponential family . We prove that the boundary (in ℂ) of every hyperbolic component is a Jordan arc, as conjectured by Eremenko and Lyubich as well as Baker and Rippon. In fact, we prove the stronger statement that the exponential bifurcation locus is connected in ℂ, an analog of Douady and Hubbard’s celebrated theorem that the Mandelbrot set is connected. We show furthermore that ∞ is not accessible through any nonhyperbolic (“queer”) stable component. The main part of the argument consists of demonstrating a general “Squeezing Lemma”, which controls the structure of parameter space near infinity. We also prove a second conjecture of Eremenko and Lyubich concerning bifurcation trees of hyperbolic components. Mathematics Subject Classification (2000)  Primary 37F10, Secondary 30D05, 37F45     

The Kirchhoff–Helmholtz integral for anisotropic elastic media

The Kirchhoff–Helmholtz integral is a powerful tool to model the scattered wavefield from a smooth interface in acoustic or isotropic elastic media due to a given incident wavefield and observation points sufficiently far away from the interface. This integral makes use of the Kirchhoff approximation of the unknown scattered wavefield and its normal derivative at the interface in terms of the corresponding quantities of the known incident field. An attractive property of the Kirchhoff–Helmholtz integral is that its asymptotic evaluation recovers the zero-order ray theory approximation of the reflected wavefield at all observation points where that theory is valid. Here, we extend the Kirchhoff–Helmholtz modeling integral to general anisotropic elastic media. It uses the natural extension of the Kirchhoff approximation of the scattered wavefield and its normal derivative for those media. The anisotropic Kirchhoff–Helmholtz integral also asymptotically provides the zero-order ray theory approximation of the reflected response from the interface. In connection with the asymptotic evaluation of the Kirchhoff–Helmholtz integral, we also derive an extension to anisotropic media of a useful decomposition formula of the geometrical spreading of a primary reflection ray.     

Eine kleine Elektrolysezelle für organische Synthesen Versuch einer Standardisierung

A versatile electrolysis cell is presented, stable to common organic solvents and easy to handle, which allows organic electrosyntheses to be performed in rather short time under conditions of low voltage, exact separation of anode and cathode compartment and good potential control. Test examples of performance are given.

     

Reagenzien

Ohne Zusammenfassung     

Electric-field dependence of muonium formation in liquid helium

The influence of electric fields on the formation of muonium in liquid helium (⁴He,³He, and mixture of⁴He + 0.2%³He) has been studied. It was found that the relative distribution of muon-electron pairs is anisotropic. The maximum muon density is shifted with respect to the electrons in the direction of the initial muon momentum. Due to the anisotropy the muonium asymmetry in normal liquid helium is enhanced by a factor of 3 in an electric fieldE=1 kV/cm.     

Neue Verbesserungen der qualitativen Schnellanalyse. II

Zusammenfassung Es wird gezeigt, daß die qualitative Schnellanalyse nicht zu einer Schematisierung der qualitativen Analyse führt, sondern diese vor neue Aufgaben stellt. Die durch die neue,Charlotsche Methode eingeführten Werte der Nachweisempfindlichkeit (Grenzkonzentrationen) geben die Möglichkeit einer vergleichenden Bewertung der drei jetzt bekannten und gebräuchlichen Methoden des qualitativen Nachweises nach der von ihnen geleisteten Arbeit und der Leistung selbst. Sie führen wieder zum Problem der Allgegenwart der Elemente nachI. undW. Noddack und unterstreichen die Bedeutung der Spurensuche für die qualitative Analyse.

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Summary It is shown that qualitative rapid analysis does not lead to a schematization of qualitative analysis, but presents the latter with new problems. The values of the limits of identification, obtained by the newCharlot method (limiting concentrations) provide the possibility of a comparison evaluation of three known and employed methods of qualitative detection by the work performed by them and the accomplishment itself. They lead once more to the problem of the omnipresence of the elements according toI. andW. Noddack and emphasize the importance of trace analysis to qualitative analysis.

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Résumé L'auteur montre que l'analyse qualitative rapide ne conduit pas à une schématisation de l'analyse qualitative mais qu'elle la place devant de nouveaux problèmes. Les limites de dilution introduites dans la nouvelle méthode deCharlot donnent la possibilité d'étudier comparativement les trois méthodes d'identification qualitative utilisables actuellement connues d'après les résultats qu'elles permettent d'obtenir et ceux de la méthode rapide. Elles conduisent de nouveau au problème de l'omniprésence des éléments d'aprèsI. etW. Noddack et mettent en évidence l'importance de la recherche des traces pour l'analyse qualitative.

     

The photoinduced triplet of flavins and its protonation states

The photogenerated triplet states of riboflavin and flavin mononucleotide (FMN) have been examined by time-resolved electron paramagnetic resonance (EPR) spectroscopy at low temperature (T = 80 K). Because of the high time resolution of the utilized EPR instrumentation, the triplets are for the first time observed in the nonequilibrated electron-spin polarized state and not in their equilibrated forms with the population of the triplet sublevels governed by Boltzmann distribution. The electron-spin polarization pattern directly reflects the anisotropy of the intersystem crossing from the excited singlet-state precursor. Spectral analysis of the resulting enhanced absorptive and emissive EPR signals yields the zero-field splitting parameters, |D| and |E|, and the zero-field populations of the triplet at high accuracy. These parameters are sensitive probes for the protonation state of the flavin's isoalloxazine ring, as becomes evident by a comparison of the spectra recorded at different pH values of the solvent. The three protonation states of the flavins can furthermore be distinguished by the kinetics of the transient EPR signals, which are dominated by spin-lattice relaxation. The fastest decays are observed for the protonated FMN and riboflavin triplets, followed by the deprotonated flavin triplets. Slow decays are measured for the triplet states of neutral FMN and riboflavin. Because proton transfer is found to be slow on the time scale of spin-polarized triplet detection by transient EPR, the pH-dependent spin-relaxation and zero-field splitting parameters offer a novel approach to probe the protonation state of flavins in their singlet ground state through the characterization of their triplet-state properties.