Review coupling of capillary electrochromatography to mass spectrometry

This review discusses the development of capillary electrochromatography (CEC) coupled to mass spectrometric (MS) detection over the last few years. Major topics addressed are instrumental setups employed and applications of this technology published in the recent literature. The instrumental section includes a discussion of the most commonly used interfaces for the hyphenation of CEC and MS as well as ionization techniques. Applications reviewed in this paper come from a variety of different fields such as the analysis of biomolecules like proteins, peptides, amino acids or carbohydrates, chiral separations or the analysis of pharmaceutical an their metabolites in a series of matrices.     

Vibrational and high pressure conformational studies of 1,1,2-trichloroethane

The infrared spectra of 1,1,2-trichloroethane were recorded from 4000 to 50 cm^?1 in the vapour and liquid states. Additional spectra above 200 cm^?1 of the low temperature crystal and of two crystalline solids, prepared by compressing the sample in a diamond anvil cell, were obtained. Also, infrared spectra of the liquid and of the compound dissolved in CS₂ were recorded at increased pressures. Raman spectral data of the liquid (including polarization measurements) and of the low temperature crystal were obtained.The fundamental frequencies for each of the two conformers, C₁ and C_s, were assigned and the results checked by normal coordinate analysis. The same diagonal and off-diagonal force constants were employed for the two conformers and the force fields were derived by means of a least squares refinement, including data for chloroethane, 1,1-dichloroethane and various deuterated species. A standard deviation of 3 % was obtained in the final fit.From the changes in relative intensities for infrared bands belonging to the C₁ and C_s conformers with increasing pressure, the volume differences (ΔV¯between the conformers were determined in CS₂ solution and in the pure liquid.     

Rare Events in Random Geometric Graphs

This work introduces and compares approaches for estimating rare-event probabilities related to the number of edges in the random geometric graph on a Poisson point process. In the one-dimensional setting, we derive closed-form expressions for a variety of conditional probabilities related to the number of edges in the random geometric graph and develop conditional Monte Carlo algorithms for estimating rare-event probabilities on this basis. We prove rigorously a reduction in variance when compared to the crude Monte Carlo estimators and illustrate the magnitude of the improvements in a simulation study. In higher dimensions, we use conditional Monte Carlo to remove the fluctuations in the estimator coming from the randomness in the Poisson number of nodes. Finally, building on conceptual insights from large-deviations theory, we illustrate that importance sampling using a Gibbsian point process can further substantially reduce the estimation variance.

     

Ergodicity of a Class of Cocycles Over Irrational Rotations

It is proved that if is irrational and L²(S¹) with o(l/n)then for each mZ\{0} the corresponding skew product is ergodic. The rigidity of specialflows over irrational rotations with roof functions whose Fouriercoefficients are in o(l/n) is also shown.     

Sur le comportement asymptotique des potentiels d'une chaîne de Markov sur ℝ d

Résumé Dans cet article j'étudie le comportement à l'infini des potentiels des chaînes de Markov sur ^d (d3) proches du mouvement brownien, tout spécialement le cas des marches aléatoires, ainsi que des critères de transience et de récurrence inspirés de la méthode utilisée.

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We study the asymptotic behaviour of potentials of Markov chains on ^d (d3), closed to Brownian motion, and particularly the case of random walks. Following a similar approach, we give transience and recurrence criteria.

     

Essential spectrum and -solutions of one-dimensional Schrödinger operators

In 1949, Hartman and Wintner showed that if the eigenvalue equations of a one-dimensional Schrödinger operator possess square integrable solutions, then the essential spectrum is nowhere dense. Furthermore, they conjectured that this statement could be improved and that under this condition the essential spectrum might always be void. This is shown to be false. It is proved that, on the contrary, every closed, nowhere dense set does occur as the essential spectrum of Schrödinger operators which satisfy the condition of existence of -solutions. The proof of this theorem is based on inverse spectral theory.

     

On the interpretation of random forces derived by projection operators

We study the derivation of a Langevin equation from a microscopic basis in order to elucidate the nature of the random force. We arrive at the conclusion that the consistent interpretation of the microscopic Langevin equation in terms of a stochastic differential equation (SDE) is according to I o rules. In addition, the random force is in general not Gaussian, and it is hence not completely characterized by its second moments.     

Trennung von V,Cr und Mn aus Stahl und Aktivierungsanalyse der Legierungselemente mit 14 MeV-Neutronen

The elements are separated from iron by solvent-extraction. Cr, V and Mn are separated by ion-exchange chromatography with a strong acidic cation-exchanger. The elements are determined by 14 MeV-neutron activation analysis using γ-spectroscopy. The method is suitable for a concentration range of 0.05 to 5%.     

pH-Dependent force spectroscopy of tri(ethylene glycol)- and methyl-terminated self-assembled monolayers adsorbed on gold

Self-assembled monolayers (SAMs) of methoxy-tri(ethylene glycol)- (EG(3)-OMe) and methyl-terminated alkanethiols (C(16)) adsorbed on polycrystalline gold were investigated by chemical force spectroscopy. Measurements were performed in aqueous electrolyte solutions depending on ionic strength and pH value. Charged and hydrophobic tips were employed as probes to mimic local patches of proteins and to study the interaction at the organic/liquid interface in detail. Force-distance curves reveal information about the origin of the observed interaction and the underlying mechanisms. The measurements confirm an effective negative surface charge to be present at the oligo(ethylene glycol) (OEG) and the methyl interface and suggest that the charges are due to the adsorption of hydroxyl ions from aqueous solution. pH-dependent measurements further support the robustness of the established charge associated with the OEG films. Its sign does not change over the whole range of investigated values between pH approximately 3.5 and approximately 10. In contrast, the hydrophobic self-assembled hexadecanethiol films on gold show an isoelectric point (IEP) around pH 4. While the mechanism of charge establishment appears to be similar for both SA films, the strength of hydrogen bonding to interfacial water, which acts as a template for hydroxyl ion adsorption, is likely to be responsible for the observed difference.