Automated and rapid online determination of 15N abundance and concentration of ammonium, nitrite, or nitrate in aqueous samples by the SPINMAS technique

On the basis of the principle of reaction continuous-flow quadrupole mass spectrometry, an automated sample preparation unit for inorganic nitrogen (SPIN) species was developed and coupled to a quadrupole Mass Spectrometer (MAS). The SPINMAS technique was designed for an automated, sensitive, and rapid determination of 15N abundance and concentration of a wide variety of N-species involved in nitrogen cycling (e.g. NH4+, NO3-, NH2OH etc.). In this paper, the SPINMAS technique is evaluated with regard to the determination of 15N abundance and concentration of the most fundamental inorganic nitrogen compounds in ecosystems such as NH4+, NO2-, and NO3-. The presented paper describes the newly developed system in detail and demonstrates the general applicability of the system. For a precise determination of 15N abundance and concentration, a minimum total N-amount of 10 microg NH4+ - N, 0.03 microg NO2- - N, or 0.3 microg NO3- - N has to be supplied. Currently, the SPINMAS technique represents the most rapid and only fully automated all-round method for a simultaneous determination of 15N abundance and total N-amount of NH4+, NO2-, or NO3- in aqueous samples.     

Signatures of non-Abelian statistics in nonlinear Coulomb blockade transport

Signatures of the non-Abelian statistics of quasiparticles in the ν=5/2 quantum Hall state are predicted to be present in the current-voltage characteristics of tunneling through one or two quantum Hall puddles of Landau filling ν(a) embedded in a bulk of filling ν(b) with (ν(a),ν(b))=(2,5/2) and (ν(a),ν(b))=(5/2,2).     

Enhancement of chloroform degradation by the combination of hydrodynamic and acoustic cavitation

The decomposition of chloroform by the combination of hydrodynamic and acoustic cavitation (Hydrodynamic-Acoustic-Cavitation/HAC) has been investigated. The flow rate and the hole diameter of the orifice plate remarkably affect the conversion of chloroform in the combined system. The conversion increases with increasing fluid velocity without any restriction. With a 2.8mm orifice plate the conversion reaches an optimal value. A synergistic effect has been obtained by the hybrid method of acoustic and hydrodynamic cavitation. The total synergistic effect achieves 17% and 73% per pass, respectively. The analysis of the energy efficiencies shows different results. Due to high optimization potential, this hybrid method can be visualized as a new step for wastewater treatment.     

Mechanisms determining the salience of coloration in echoed sound: influence of interaural time and level differences

This study investigates whether the salience of the pitch associated with a single reflection of a broadband sound, such as noise, is determined by the monaural information mediated by the stimuli at the two ears, or by the relative locations of the primary sound and the reflection. Pitch strength was measured as a function of the reflection delay and the lateral displacement between the primary sound and the reflection. Thereby, lateral displacement was produced by means of interaural time differences (ITDs) in experiment 1 and interaural level differences (ILDs) in experiment 3. The results from both experiments are in accordance with the assumption that the strength of the pitch associated with a reflection is based on a central average of the internal representations of the stimuli at the two ears. This notion was corroborated by experiment 2, which showed that the results from experiment 1 could be mimicked by simply adding the stimuli from the two ears and presenting the merged stimulus identically to both ears.     

Proton-detected scalar coupling based assignment strategies in MAS solid-state NMR spectroscopy applied to perdeuterated proteins

Assignment of proteins in MAS (magic angle spinning) solid-state NMR relies so far on correlations among heteronuclei. This strategy is based on well dispersed resonances in the ¹⁵N dimension. In many complex cases like membrane proteins or amyloid fibrils, an additional frequency dimension is desirable in order to spread the amide resonances. We show here that proton detected HNCO, HNCA, and HNCACB type experiments can successfully be implemented in the solid-state. Coherences are sufficiently long lived to allow pulse schemes of a duration greater than 70 ms before incrementation of the first indirect dimension. The achieved resolution is comparable to the resolution obtained in solution-state NMR experiments. We demonstrate the experiments using a triply labeled sample of the SH3 domain of chicken α-spectrin, which was re-crystallized in H₂O/D₂O using a ratio of 1/9. We employ paramagnetic relaxation enhancement (PRE) using EDTA chelated Cu^II to enable rapid data acquisition.     

The effect of oxidation on the surface-near lattice relaxation in FeNi nanoparticles

The near-surface oxidation-induced lattice relaxation and compositional changes of FeNi alloy nano-particles are investigated. Using a newly developed transfer system, the particle structure was characterised by means of aberration-corrected HR-TEM prior to exposing the particles to ambient air. This allows for a comparison of oxidised and un-oxidised particles, respectively. Independent of the oxidation, the surface-near and/or interface-near metal lattice was found to be expanded by up to 3%. EELS profiles clearly reveal an enrichment of Fe at the particle surfaces. MD simulations in combination with HR-TEM contrast simulations were conducted to investigate the effect of the Fe enrichment on the structural relaxation. The results show that a surface-near over-stoichiometric enrichment of Fe indeed causes a dilation that counteracts a compression of the lattice at the particle surface as obtained for homogeneously alloyed particles. Besides, the large lattice mismatch between the metallic cores and the NiFe₂O₄ shells causes the formation of step dislocations in the close vicinities of the interface. In essence, the surface-near lattice relaxation in oxide free particles is found to be due to a segregation of Fe to the surface, whereas in the case of shell–core particles, no systematic influence of the oxide on the lattice relaxation was found.     

Signature of a type-a glass transition and intrinsic confinement effects in a binary glass-forming system

We study dynamically highly asymmetric binary mixtures comprised of small methyl tetrahydrofuran (MTHF) molecules and polystyrene. Combined use of dielectric spectroscopy, ^{2}H nuclear magnetic resonance, incoherent quasielastic neutron scattering, and depolarized dynamic light scattering allows us to selectively probe the dynamics of the components in a broad dynamic range. It turns out that the mixtures exhibit two glass transitions in a wide concentration range although being fully miscible on a macroscopic scale. In between both glass transition temperatures, the dynamics of the small molecules show strong confinement effects, e.g., a crossover from Vogel-Fulcher to Arrhenius behavior of the time constants. Moreover, the dynamical behavior of small molecules close to the slow matrix is consistent with mode coupling theory predictions for a type-A glass transition, which was expected from recent theoretical and simulation studies in comparable systems.     

Cross-approximate entropy of cortical local field potentials quantifies effects of anesthesia - a pilot study in rats

Background

Anesthetics dose-dependently shift electroencephalographic (EEG) activity towards high-amplitude, slow rhythms, indicative of a synchronization of neuronal activity in thalamocortical networks. Additionally, they uncouple brain areas in higher (gamma) frequency ranges possibly underlying conscious perception. It is currently thought that both effects may impair brain function by impeding proper information exchange between cortical areas. But what happens at the local network level? Local networks with strong excitatory interconnections may be more resilient towards global changes in brain rhythms, but depend heavily on locally projecting, inhibitory interneurons. As anesthetics bias cortical networks towards inhibition, we hypothesized that they may cause excessive synchrony and compromise information processing already on a small spatial scale. Using a recently introduced measure of signal independence, cross-approximate entropy (XApEn), we investigated to what degree anesthetics synchronized local cortical network activity. We recorded local field potentials (LFP) from the somatosensory cortex of three rats chronically implanted with multielectrode arrays and compared activity patterns under control (awake state) with those at increasing concentrations of isoflurane, enflurane and halothane.

Results

Cortical LFP signals were more synchronous, as expressed by XApEn, in the presence of anesthetics. Specifically, XApEn was a monotonously declining function of anesthetic concentration. Isoflurane and enflurane were indistinguishable; at a concentration of 1 MAC (the minimum alveolar concentration required to suppress movement in response to noxious stimuli in 50% of subjects) both volatile agents reduced XApEn by about 70%, whereas halothane was less potent (50% reduction).

Conclusions

The results suggest that anesthetics strongly diminish the independence of operation of local cortical neuronal populations, and that the quantification of these effects in terms of XApEn has a similar discriminatory power as changes of spontaneous action potential rates. Thus, XApEn of field potentials recorded from local cortical networks provides valuable information on the anesthetic state of the brain.

     

Quantum pharmacological studies on antimalarial drugs

Summary Linear models for the relation between electronic structure and antimalarial activity of chloroquine drugs have been investigated, based on CNDO/2 molecular orbital calculations. The results indicate that changes in electron density on the atoms N1, N2, C4, C9, and C10 have the strongest influence on the pharmacological activity, so that these atoms can be assumed to form the main active center of these drugs. Correlations improve, if substitution on the nucleus of chloroquine and side chain variations are treated separately. The models found seem to be a useful tool for designing new drugs within the chloroquine series.

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Quantenchemisch-pharmakologische Untersuchungen von Antimalaria-Wirkstoffen

Zusammenfassung Auf der Basis von CNDO/2-Rechnungen wurden lineare Modelle für die Relation zwischen Elektronenverteilung und der Antimalaria-Aktivität von Chlorochinen untersucht. Es zeigte sich, daß Veränderungen in den Elektronendichten der Atome N1, N2, C4, C9 und C10 den stärksten Einfluß auf die pharmakologische Wirkung haben. Es kann somit angenommen werden, daß diese Atome die hauptsächlich aktiven Zentren der Verbindung sind. Die Korrelation wird verbessert, wenn die Substitution am Chlorochin-Kern und Variationen der Seitenketten separat behandelt werden. Die aufgefundenen Modellvorstellungen sollten ein nützliches Werkzeug zur gezielten Synthese neuer Wirkstoffe innerhalb der Chlorochin-Reihe darstellen.

     

Comparison of cartesian and lobe function Gaussian basis sets

The lobe function and cartesian (spherical harmonic) gaussian are compared with reference to calculations for second-row atoms. Single and grouped gaussian basis sets which have been reported for cartesian functions are taken over directly to construct corresponding lobe function bases with identical sets of exponents and with lobe separations chosen by a scaling procedure. Total and orbital energies and SCF coefficients resulting from calculations on the second-row atoms using the two types of functions for both primitive and grouped gaussian basis sets are seen to be in excellent agreement, thereby emphasizing the essential equivalence of lobe functions and cartesian gaussians, at the very least with respect to calculation of energy surfaces.

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Zusammenfassung Die Lobe-Funktionen und kartesischen (Kugelfunktions-) Gaußfunktionen werden in Berechnungen von Atomen der zweiten Reihe des periodischen Systems verglichen. Schon bekannte einfache und gruppierte Gaußfunktionsbasissätze für kartesische Funktionen werden direkt übernommen, um entsprechende Lobe-Funktionsbasen mit identischen Exponenten zu konstruieren, wobei die zugehörigen Lobe-Abstände nach einer Koordinatenstreckungs-(scaling) Methode berechnet werden. Gesamt- und Orbitalenergien sowie SCF-Koeffizienten für die Atome der zweiten Reihe stimmen bei Benutzung der beiden verschiedenen Funktionstypen, sowohl bei einfacher als auch bei gruppierter Gaußfunktionsbasis, außerordentlich gut überein, wodurch die wesentliche Gleichwertigkeit von Lobe-Funktionen und kartesischen Gaußfunktionen betont wird, zum allermindesten hinsichtlich der Berechnung von Energieflächen.

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Résumé La fonction de lobe et la gaussienne cartésienne (harmonique sphérique) sont comparées sur des calculs d'atomes de la seconde ligne. Des bases de gaussiennes simples et groupées utilisées pour les fonctions cartésiennes sont directement employées pour construire les bases correspondantes de fonctions à lobes avec des ensembles d'exposants identiques et des séparations de lobes choisis par calibrage. L'emploi de ces deux types de fonctions donne des résultats concordants pour l'énergie totale, les énergies orbitales et les coefficients SCF, mettant l'accent sur l'équivalence essentielle des fonctions à lobe et des gaussiennes cartésiennes, tout au moins pour le calcul des surfaces d'énergie.