Adsorptive Stripping Voltammetric Determination of 2,4-Dichlorophenol by Laponite Modified Carbon Paste Electrode

A laponite modified carbon paste electrode was prepared, characterized and applied for the 2,4-dichlorophenol (2,4-DCP) voltammetric determination. It takes advantage of the ability of laponite to adsorb phenols, as well as of its availability and very low cost. Kinetic and equilibrium data for 2,4-DCP adsorption by laponite in aqueous dispersions demonstrated that the adsorption process obeyed a pseudo first order kinetic model and was consistent with the formation of adsorbed multilayers on a surface with heterogeneous pore distribution. The composite paste electrode exhibited a heterogeneous surface with 65 % increased surface area and 27 % enhanced catalytic activity compared to the unmodified one. The adsorptive stripping voltammetric determination of 2,4-DCP at an electrode with an optimized graphite:laponite ratio of 55 : 15 w% using a 3 min accumulation time at pH 5.5 was found to be suitable for its quantification in the linear concentration range extended up to 50 μmol L⁻¹ with a sensitivity of 0.56 μA L μmol⁻¹ and a LOD of 0.2 μmol L⁻¹ (S/N=3).The 2,4-DCP electrochemical response was not affected by the presence of some structurally similar phenols, like catechol and p-nitrophenol, while resorcinol, 2-chlorophenol, and 4-chlorophenol presented interferences. The results were validated by 2,4-DCP determination in spiked tap water.     

Zur Zerfallskonstanten der inneren Konversion von 99mTc im metallischen Zustand

In der Skala der Zerfallskonstanten für die innere Konversion von ^99mTc weisen gerade die Meβwerte für die metallischen Proben eine ungewöhnlich groβe Streuung auf. Einige Messungen enthüllen einen Zusammenhang zwischen dieser Streuung und einigen Probenparametern (Schichtdieke, Homogenitāt, Grad der durchgeführten Reduktion). Auf der Grundlage eines theoretischen Streuwellenbildes für die chemischen Effekte auf die innere Konversion von ^99m Tc wird nun verstāndlich, daβ alle Unzulānglichkeiten bei der Probenprāparation den Meβwert in eine Richtung verschieben. So wird mit Hilfe der Messung der Zerfallskonstanten der inneren Konversion von ^99mTc eine Bewertung der Güle dünner metallischer Technetiumschichten möglich.

In the pattern of decay constants for the internal conversion of ^99mTc, just the measured values of metallic samples are subject to unusually high scattering. Own measurements reveal an interdependence between this scattering and some sample parameters (thickness of layers, homogeneity, degree of conducted reduction). On the basis of a theoretical scattered wave pattern for the chemical effects on the internal conversion of ^99mTc it is becoming clear, that any deficiencies in sample preparation shift the measured values towards some direction. So, measurement of decay constants of the internal conversion of ^99mTc renders possible an estimation of the quality of thin metallic technetium layers.     

Molecular Dynamics of Polymer Composites Using Rheology and Combined RheoNMR on the Example of TiO2-Filled Poly(n-Alkyl Methacrylates) and Trans-1,4-Polyisoprene

The determination of the interplay between polymeric matrices and filler particles in composites is of great interest to understand structure-property relationships and develop predictive theories. To study the molecular dynamics of polymers in composites, model systems based on poly(n-alkyl methacrylates), trans-1,4-polyisoprene (gutta percha), and titania (TiO₂) were prepared and characterized using rheometry and a combined RheoNMR technique. Apparent entanglement molecular weights were obtained from small amplitude oscillatory shear (SAOS) experiments, which are related to the increasing physical cross-link density as a function of the filler content. Large amplitude oscillatory shear (LAOS) experiments were performed and analyzed within the FT-rheometry framework. The filler had a strong impact on the scaling behavior of the normalized third harmonic. A combined RheoNMR technique was used to simultaneously study the molecular dynamics via NMR and the corresponding mechanical response via rheometry. A strong correlation between the macroscopic mechanical properties and microscopic molecular dynamics was found, which might lead to a new understanding of polymer melt dynamics.     

Approximated algorithms for the minimum dilation triangulation problem

The complexity status of the minimum dilation triangulation (MDT) problem for a general point set is unknown. Therefore, we focus on the development of approximated algorithms to find high quality triangulations of minimum dilation. For an initial approach, we design a greedy strategy able to obtain approximate solutions to the optimal ones in a simple way. We also propose an operator to generate the neighborhood which is used in different algorithms: Local Search, Iterated Local Search, and Simulated Annealing. Besides, we present an algorithm called Random Local Search where good and bad solutions are accepted using the previous mentioned operator. For the experimental study we have created a set of problem instances since no reference to benchmarks for these problems were found in the literature. We use the sequential parameter optimization toolbox for tuning the parameters of the SA algorithm. We compare our results with those obtained by the OV-MDT algorithm that uses the obstacle value to sort the edges in the constructive process. This is the only available algorithm found in the literature. Through the experimental evaluation and statistical analysis, we assess the performance of the proposed algorithms using this operator.     

Two‐step synthesis of new 1,2,4,5‐tetrahydrospiro‐[3H‐2‐benzazepine‐3,4′‐piperidines] from 4‐iminopiperidines

New spiro[3H‐2‐benzazepine‐3,4′‐piperidines] and their precursors, N‐substituted 4‐allyl‐4‐N‐benzyl‐aminopiperidines, have been prepared as potential psychotic agents from readily available 4‐iminopiperidines, by a sequence of reactions that included nucleophilic addition of Grignard reagents and Bronsted acid‐mediated intramolecular cyclisation. Some of the compounds prepared have been tested in albine mice for spontaneous motor activity. All compounds prepared were characterized by ir and ¹H nmr spectroscopies and cg‐ms spectrometry.     

Erste Ergebnisse zur Anwendung der prompten Gammastrahlung im Hinblick auf die vor Ort Anwendung in der Bauzustandsanalyse

Im Hinblick auf eine vor Ort Anwendung auf dem Gebiet der Bauwerksdiagnostik stellt die vorliegende Arbeit erste Ergebnissc vor, die unter Ausnutzung der prompten Gammastrahlung erzielt wurden. Dabei werden ausschlieβlich, unelastische Streuprozesse schneller Neutronen an der Probenmatrix betrachtet. Dic Anregung erfolgte mit einer ²³⁸Pu/Be-Neutronenquelle mit einem Neutronenfluβ von ca. 5 × 10⁷ s^?1 und die Registrierung der prompten Gammastrahlung mit einem NaI(Tl)-Kristall. Besonderes Augenmerk galt den Elementen Mg, Al, Si und Fe als qualitätsbeeinflussende Parameter des Betons.

This publication is a contribution to the application of nuclear metltods in civil engineering. In view of in situ determination of elements in walls of concrete the first results of applying prompt gamma radiation, due to inelastic scattering of fast neutrons in the sample are shown. The stimulation of prompt gamma-rays is carried out by means of a ²³⁸Pu/Bneutron source with a flux of neutrons of about 5 × 10⁷ s^?1 and the detection of gamma radiation by means of a Nal(Tl)- deteclor. The elements Mg, Al, Si and Fe as the parameters of quality of concrete were the elements of interest.     

The model of the black hole enclosed in dust: the flat space case

The model is constructed to describe the Schwarzschild-like black hole enclosed in the dust cosmological background. It is an exact solution of Einstein equations for spherically symmetric dust distribution, and is a special case of Lemaitre–Tolman–Bondi solutions. The motion of the test particle in the model is investigated in comoving coordinate frame. Observable velocity of the particle is found from geodesic equations. It is shown that chosen reference system does not allow to solve the problem of ’all or nothing’ behavior.     

SEC‐MR‐NMR: Online Coupling of Size Exclusion Chromatography and Medium Resolution NMR Spectroscopy

Online coupling of size exclusion chromatography together with medium resolution nuclear magnetic resonance (SEC‐MR‐NMR) might be one solution to the problem of chemically sensitive detection in liquid polymer chromatography. By use of a combination of SEC with a table‐top, specially designed 20 MHz NMR spectrometer, based on a permanent magnet, online ¹H NMR spectra of SEC fractions can be obtained. The integration of digital filters, mechanical shims and electronic shims led to substantially improved sensitivity and chemical selectivity compared to former TD (time domain) 20 MHz instruments. ¹H NMR spectra of PMMA and PS homopolymers as well as PS‐PMMA block copolymers were of sufficient quality to enable detection and de‐formulation of unknown polymer compounds. ¹H NMR spectra of acceptable resolution and S/N ratio were collected online during the chromatography. The SEC separation online with the NMR measurements performed well and resulted in the proof of principle of the SEC‐MR‐NMR combination.