Zur Problematik individueller thermodynamischer Aktivitätskoeffizienten einzelner Ionensorten in Elektrolytlösungen hoher Konzentration

On the Individual Thermodynamic Activity Coefficients of Single Ion Species in Electrolyte Solutions at High Concentrations The individual activity coefficients of the single ion species, which are produced by dissociation of aqueous electrolytes, are necessary for the thermodynamic treatment of equilibrations and processes involving electrolytes. The determination of these values is one of the basic quests of electrochemistry and a controversial topic. This problem is unsolvable using classical thermodynamics. In this paper a mathematical method is shown, which can be used to split the mean activity coefficients into the values for the individual ion species of an electrolyte. For this determination the mean activity coefficients have to be expressed in the power form of equation. The concept based on the adaptation of a product function for the concentration development of the mean activity coefficients to the experimental data and their separation into factor functions of a predefined structure, which represent the concentration development of the individual activity coefficients of the single ion species of the electrolyte. This mathematical method was used to calculate the individual activity coefficients of the single ion species of alkali chlorides, alkaline earth chlorides, alkaline earth perchlorates, hydrohalic acids and alkali hydroxides. In summary, all the calculated single ion activity coefficients are in good agreement with the expected theoretical considerations. A proportionality to the reciprocal diameter of the unhydrated cation is clearly recognizable. The calculated individual activity coefficients correspond in every case with the assumption about their size, which can be reproduced using a variety of electrochemical investigations and experiments.     

Ein verbessertes Kautschuk-L?throhrgebl?se

Ohne Zusammenfassung     

Direct electrochemistry of cytochrome c on nanotextured diamond surface

Nanotextured diamond surfaces with geometrical properties close to protein dimensions were used for the realization of direct electron transfer of cytochrome c (cyt c) without any covalent bonding. The peroxidase activity of native and denatured cyt c was also investigated. Cyclic voltammograms of native cyt c show quasi-reversible electron transfer reactions, while no heme redox activity is detected for denatured cyt c. Unfolding (denaturation) of cyt c can be achieved in the presence of hydrogen peroxide. Partially or fully denatured cyt c showed higher peroxidase activity than native cyt c. This is because denatured cyt c loses its tertiary structure and hydrogen peroxide is easier to access the heme redox center. The apparent Michaelis–Menten constant K_m for native and denatured cyt c has been determined to be 0.23 mM and 0.08 mM.     

Phase I and II metabolites of speciogynine, a diastereomer of the main Kratom alkaloid mitragynine, identified in rat and human urine by liquid chromatography coupled to low- and high-resolution linear ion trap mass spectrometry

Mitragyna speciosa (Kratom in Thai), a Thai medical plant, is misused as herbal drug of abuse. Besides the most abundant alkaloids mitragynine (MG) and paynantheine (PAY), several other alkaloids were isolated from Kratom leaves, among them the third abundant alkaloid is speciogynine (SG), a diastereomer of MG. The aim of this present study was to identify the phase I and II metabolites of SG in rat urine after the administration of a rather high dose of the pure alkaloid and then to confirm these findings using human urine samples after Kratom use. The applied liquid chromatography coupled to low- and high-resolution mass spectrometry (LC-HRMS-MS) provided detailed information on the structure in the MS(n) mode particularly with high resolution. For the analysis of the human samples, the LC separation had to be improved markedly allowing the separation of SG and its metabolites from its diastereomer MG and its metabolites. In analogy to MG, besides SG, nine phase I and eight phase II metabolites could be identified in rat urine, but only three phase I and five phase II metabolites in human urine. These differences may be caused by the lower SG dose applied by the user of Kratom preparations. SG and its metabolites could be differentiated in the human samples from the diastereomeric MG and its metabolites comparing the different retention times determined after application of the single alkaloids to rats. In addition, some differences in MS(2) and/or MS(3) spectra of the corresponding diastereomers were observed.     

Hydrogen Production by Water Dissociation in Surface‐Modified BaCoxFeyZr1−x−yO3−δ Hollow‐Fiber Membrane Reactor with Improved Oxygen Permeation

A porous perovskite BaCo_xFe_yZr_0.9?x?yPd_0.1O_3?δ (BCFZ‐Pd) coating was deposited onto the outer surface of a BaCo_xFe_yZr_1?x?yO_3?δ (BCFZ) perovskite hollow‐fiber membrane. The surface morphology of the modified BCFZ fiber was characterized by scanning electron microscopy (SEM), indicating the formation of a BCFZ‐Pd porous layer on the outer surface of a dense BCFZ hollow‐fiber membrane. The oxygen permeation flux of the BCFZ membrane with a BCFZ‐Pd porous layer increased 3.5 times more than that of the blank BCFZ membrane when feeding reactive CH₄ onto the permeation side of the membrane. The blank BCFZ membrane and surface‐modified BCFZ membrane were used as reactors to shift the equilibrium of thermal water dissociation for hydrogen production because they allow the selective removal of the produced oxygen from the water dissociation system. It was found that the hydrogen production rate increased from 0.7 to 2.1 mL H₂ min^?1 cm^?2 at 950 °C after depositing a BCFZ‐Pd porous layer onto the BCFZ membrane.     

Stereophotogrammetric 3D shape measurement by holographic methods using structured speckle illumination combined with interferometry

We present a unique combination of the numerical three-dimensional (3D) reconstruction of the shape of an object with interferometric deformation measurements. Two cameras record several holograms of an object that is illuminated by structured illumination. This illumination is realized by speckle patterns. To improve the image quality, an inplace speckle reduction technique is combined with the structured illumination to reduce the effect of disturbing subjective speckles which appear in the reconstructed images. Stereophotogrammetric methods are applied to extract the 3D surface information of the object out of the reconstructed images. Since the recording is done by holography and because stereophotogrammetry enables a pointwise correlation between the two views, it is possible to combine other holographic techniques with the reconstructed 3D shape. This is demonstrated by an interferometric deformation measurement of an object cooling down. The resulting interferometric fringes are mapped onto the reconstructed 3D surface. Hence, the proposed method enables automatic and dense matching of interferometric fringe-maps recorded by spatially separated holograms onto the surface of the object, which has not yet been realized by existing techniques.     

On spurious and corrupted multifractality: The effects of additive noise, short-term memory and periodic trends

We study the performance of multifractal detrended fluctuation analysis (MF-DFA) applied to long-term correlated and multifractal data records in the presence of additive white noise, short-term memory and periodicities. Such additions and disturbances that can be typically found in the observational records of various complex systems ranging from climate dynamics to physiology, network traffic, and finance. In monofractal records, we find that (i) additive white noise hardly results in spurious multifractality, but causes underestimated generalized Hurst exponents h(q) for all q values; (ii) short-range correlations lead to pronounced crossovers in the generalized fluctuation functions F_q(s) at positions that decrease with increasing moment q, thus causing significantly overestimated h(q) for small q and spurious multifractality; (iii) periodicities like seasonal trends (with standard deviations comparable with the one of the studied process) result in spurious “reversed” multifractality where h(q) increases with increasing q (except for very short time windows). We also show that in multifractal cascades moderate additions of noise, short-range memory, or periodic trends cause flawed results for h(q) with q<2, while h(q) with q>2 remains nearly unchanged.     

Variational Approach to Fourth-Order Impulsive Differential Equations with Two Control Parameters

In this paper, we are concerned with the multiplicity of solutions for a fourth-order impulsive differential equation with Dirichlet boundary conditions and two control parameters. Using variational methods and a three critical points theorem, we give some new criteria to guarantee that the impulsive problem has at least three classical solutions. We also provide an example in order to illustrate the main abstract results of this paper.