Quantitative Bestimmungen mittels cyclischer Voltammetrie an der Phasengrenze zweier mischbarer Elektrolytl?sungen

Summary This paper presents some applications of cyclic voltammetry at the interface of two immiscible electrolyte solutions by means of an experimental set-up described in a former publication. When using special sample preparation good results are obtained for the determination of iodide and quinine in pharmaceutical products as well as for the determination of quinine in tonic water and dodecylsulfate in a tooth-salt.

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Herrn Prof. Dr. Günther Tölg zum 60. Geburtstag gewidmet     

On the onset of separation in turbulent boundary layer flow over two-dimensional humps of various size

Summary The available laboratory data of turbulent boundary layer flow over two-dimensional obstacles have been examined in order to identify the parameters (such as the aspect ratio or the surface roughness) driving the onset of separation. A comparison with some linearized models suitable for atmospheric applications is also made. It results that i) the model response can be highly sensitive to the detailed shape of the obstacle; ii) the ratio between obstacle length and boundary layer thickness is relevant in determining the pressure perturbation near the surface; iii) the surface shear stress is poorly described in most cases and in particular in the obstacle wake.

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Riassunto I dati di laboratorio disponibili, relativi a strati limite turbolenti su ostacoli bidimensionali, sono stati esaminati al fine di identificare i parametri guida della separazione (quali la pendenza o la rugosità della superficie). Inoltre è stato fatto un confronto con i risultati di alcuni modelli linearizzati adatti per applicazioni atmosferiche. Ne risulta che i) la risposta del modello è molto sensibile alla forma dettagliata dell’ostacolo; ii) il rapporto fra la lunghezza dell’ostacolo e lo spessore dello strato limite turbolento incidente è importante nel determinare la perturbazione della pressione vicino alla superficie; iii) lo ?shear stress? superficiale non è riprodotto con accuratezza nella maggioranza dei casi, in particolare nella scia dell’ostacolo.

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Резюме Анализируются имеющиеся лабораторные данные по турбулентному течению в пограничном слое над двумерными препятствиями, чтобы идентифицировать параметры (такие как аспектное отношение или шероховатость поверхности), определяющие возникновение отрыва. Проводится сравнение с некоторыми линеаризованными моделями, удобными для атмосферных приложений. Получены следующие результаты: 1) модельный отклик может быть очень чувствительным к детальной форме препятствия; 2) отношение между длиной препятствия и толщиной поверхностного слоя является существенным при определении возмущения давления вблизи поверхности; 3) напряжение поверхностного сдвига плохо описывается в большинстве случаев и, в частности, в спутной струе.

     

Assay of vecuronium in plasma using solid-phase extraction, high-performance liquid chromatography and post-column ion-pair extraction with fluorimetric detection

An assay has been developed and validated for the routine monitoring of vecuronium in plasma. It consists of solid-phase extraction using C18 disposables as sample pre-treatment, high-performance liquid chromatography and post-column ion-pair extraction with fluorimetric detection. The fluorescent anion 9,10-dimethoxyanthracene-2-sulphonate (DAS) is used as the counter ion. The detection limit is ca. 5 ng/ml in plasma with a signal-to-noise ratio of 10. The assay is also applicable for monitoring vecuronium and its potential metabolites in other biological media, e.g., urine, bile and tissue (liver, kidney) homogenates.     

Bulk and microprobe analysis for trace elements with synchrotron radiation

Blood serum samples were irradiated by monochromatic synchrotron radiation (15 keV) and by 2.4-MeV protons to compare their performance for the detection of trace elements by x-ray fluorescence (XRF) spectrometry. Absolute concentration assignment was based on the addition of an internal standard and on a method which uses the incoherent and coherent radiation as a flux monitor of the incoming beam. Preliminary experiments with a synchrotron XRF microprobe are reported.     

Synthesis of novel 2-perfluoroacylcyclohexane-1,3-diones

A one-pot synthesis of 2-perfluoroalkanoylcyclohexane-1,3-diones via C-acylation of cyclohexane-1,3-diones with N-perfluoroacylimidazole as an acylating agent is reported. A reaction was examined with isolated N-trifluoroacetylimidazole and with N-perfluoroacylimidazoles generated in situ from perfluorocarboxylic acid anhydrides or perfluorocarboxylic acids.     

A topological analysis of electron density and chemical bonding in cyclophosphazenes PnNnX2n (X = H, F, Cl; n = 2, 3, 4)

The restricted Hartree-Fock method was used to determine the cycle size effects on the geometric parameters of several inorganic templates, cyclophosphazenes P_nN_nX_2n (X = H, F, Cl; n = 2, 3, 4). A topological analysis of local electronic properties at the electron density critical points of bonds allowed us to quantitatively characterize the chemical bond in cyclophosphazenes and its dependence on the cycle size and substituents at phosphorus. The calculated distributions of the electron density Laplacian and electron pair localization functions revealed the special features of the electronic structure of the nitrogen and phosphorus atoms. These results explain the nature of noncovalent interactions between the P atoms of one cyclophosphazene molecule and the N atoms of the other.