Umsetzungen fester Stoffe in Lösungen, 1. Mitt.: Reaktion BaSO4 fest+K2CO3 gelöst=BaCO3 fest+K2SO4 gelöst

Zusammenfassung Die Reaktionsgeschwindigkeit der im Titel genannten Umsetzung wurde bei verschiedenen Temperaturen und Konzentrationen gemessen. In beiden Fällen konnte man die Gleichungen vonJander und vonGinstling für die Diffusions-Reaktionskinetik anwenden. Die Aktivierungsenergie ist 26±2 kcal/gMol. Die Reaktionsgeschwindigkeit wächst exponentiell mit der K₂CO₃-Konzentration. Die spezif. Oberfläche der festen Phase verkleinert sich etwas nach verschiedenen Reaktionszeiten, BaSO₄ selbst zeigt aber eine stärkere Verkleinerung seiner Oberfläche während der Reaktion.

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The reaction rate has been measured at various temperatures and concentrations. It has been shown that in both cases the equations of diffusion reaction kinetics ofJander and ofGinstling can be applied. Activation energy was determined 26±2 kcal/g-mol. The reaction rate has been found to be exponentially proportional to the concentration of K₂CO₃. Surface measurements of the solid phase following successive reaction times show a gentle decrease, whereas BaSO₄ alone displays a strong decrease of surface as a function of the degree of conversion.

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Mit 6 Abbildungen     

Syntheses and vibrational spectra of xenon(VI) fluorozirconate(IV) and xenon(VI) fluorohafnate(IV)

Liquid xenon difluoride at 140°C does not react with zirconium or hafnium tetrafluorides, neither does liquid xenon hexafluoride at 60°C. Therefore reactions between the corresponding hydrazinium fluorometalates or ammonium fluorometalates and xenon difluoride and xenon hexafluoride, respectively, were carried out. N₂H₆ZrF₆ and N₂H₆HfF₆ react with xenon difluoride at 60°C again yielding only the corresponding tetrafluorides, while the analogous reaction with (NH₄)₂ZrF₆ and (NH₄)₂HfF₆ proceeds at 170°C yielding the corresponding ammonium pentafluorometalates, which are stable and do not react further with excessive xenon difluoride up to 200°C.The reaction between N₂H₆ZrF₆ or N₂H₆HfF₆ and xenon hexafluoride proceeds at room temperature yielding a series of thermally unstable compounds of the type mXeF₆.MF₄ (M = Zr, Hf) where m ? 6. The final products which are stable at room temperature are XeF₆.MF₄ (M = Zr,Hf). Spectroscopic evidence suggests that these compounds are salts of a XeF⁺₅ cation squashed between a polymeric anion of the type (MF₅)^x-_x.     

Reactive oxygen species (ROS) generation inhibited by aporphine and phenanthrene alkaloids semi-synthesized from natural boldine

Four phenanthrene and one aporphine alkaloids semi-synthesized from boldine were evaluated for their inhibitory effect on reactive oxygen species (ROS) generation. ROS generation by neutrophils stimulated with N-formyl-methionyl-leucyl-phenylalanine was inhibited in a concentration dependent manner. Alkaloids exerted similar inhibitory effect in the hypoxanthine-xanthine oxidase system than in stimulated neutrophils, which could be attributed to a direct ROS scavenging activity. None of the alkaloids assayed had any effect on xanthine oxidase activity. Therefore the synthesized alkaloids might constitute an alternative therapy in inflammation disorders in which ROS generation is involved.     

Estimation of stability constants of copper(II) and nickel(II) chelates with dipeptides by using topological indices

The estimation of the overall stability constants β₁ of copper(II) and nickel(II) chelates with dipeptides was performed by using the model with the valence connectivity index of the 3rd order (³χ^v). It was done by dividing β₁ to its constituting constants K₁ and K_a, and subsequently by dividing the basic set into subsets or treating the chelate rings as separate units. Altogether 15 copper(II) and eight nickel(II) chelates with dipeptides were investigated. Six models for the estimation of log K₁ and pK_a were checked, most of them by usage of indicator variables (for differentiation of copper(II) and nickel(II) complexes or subclasses of ligands). Estimates of log β₁ gave the range of rms values from 0.19 to 0.27. For the best model, errors of estimates were less than 0.34.     

The Quest for Molecular Grippers: Photo-Electric Control of Molecular Gripping Machinery

The quest for nanoscale molecular machines has inspired the search for their close relatives, molecular grippers. This path was paved by the development of resorcin[4]arene cavitands and their quinone-based redox-active congeners. In this Concept article, the efforts to design and establish the control of quinone-functionalized resorcin[4]arenes by electronic and electromagnetic stimuli is described. This was achieved by relying on paramagnetic semiquinone radical anions formed electrochemically or by photoredox catalysis. The gripper-like motion of such species could not be studied by conventional NMR spectroscopy. Instead, an entirely different approach had to be developed that included various electroanalytical and spectroelectrochemical methods, including UV/Vis/NIR spectroelectrochemistry, pulsed EPR and Davies ¹H ENDOR spectroscopy, transient absorption spectroscopy, and time-resolved luminescence measurements, besides density functional theory calculations and X-ray crystallography. The conceptual breakthroughs are reviewed as well as the current state and future perspectives of photoredox-switchable molecular grippers.     

The Rise of Dye-Sensitized Solar Cells: From Molecular Photovoltaics to Emerging Solid-State Photovoltaic Technologies

Over the past three decades, dye-sensitized solar cells (i. e. Grätzel cells) have evolved from a pioneering concept of molecular photovoltaics to large-scale industrial deployment. In this review article, we provide a historical overview of the developments with a focus on the scientific advancements that have set the stage for this technology to emerge and thrive. This involves insights into the (photo)electrochemistry of the underlying processes, molecular engineering of dyes, redox shuttles, and hole-transporting materials, as well as their implementation into solar cells. We further outline applications and future perspectives, involving the long-lasting objective to develop efficient solid-state alternatives to conventional dye-sensitized solar cells.     

Chalcogen Bonding “2S–2N Squares” versus Competing Interactions: Exploring the Recognition Properties of Sulfur

Chalcogen bonding (CB) is the focus of increased attention for its applications in medicinal chemistry, materials science, and crystal engineering. However, the origin of sulfur's recognition properties remains controversial, and experimental evidence for supporting theories is still emerging. Here, a comprehensive evaluation of sulfur CB interactions is presented by investigating 2,1,3-benzothiadiazole X-ray crystallographic structures gathered from the Cambridge Structure Database (CSD), Protein Data Bank (PDB), and own laboratory findings. Through the systematic analysis of substituent effects on a subset library of over thirty benzothiadiazole derivatives, the competing interactions have been categorized into four main classes, namely 2S–2N CB square, halogen bonding (XB), S ⋅⋅⋅ S, and hydrogen-bonding (HB). A geometric model is employed to characterize the 2S–2N CB square motifs and discuss the role of electrostatic, dipole, and orbital contributions toward the interaction.     

“What Counts as an Insult?”

In virtue of what does a linguistic act count as an insult? I discuss five main approaches to this question, according to which an insult is determined by (i) the semantic properties of the expression used; (ii) the insulter, her intention, or attitudes; (iii) the addressee and her personal standard; (iv) the features of the speech act performed; and (v) the standard of the relevant social group. I endorse the last, objectivist account, according to which an act x counts as an insult if and only if x is assessed as demeaning when addressed at A by the standard of the relevant social group at t.     

Synthesis and anthelmintic activity of benzopyrano[2,3-c]pyrazol-4(2H)-one derivatives

Molecular Diversity - A series of benzopyrano[2,3-c]pyrazol-4(2H)-one derivatives were synthesized from readily available 1-phenyl- and 1-methyl-1H-pyrazol-3-ols by sequentially employing...     

Some applications of smooth bilinear forms with Kloosterman sums

We revisit a recent bound of I. Shparlinski and T. Zhang on bilinear forms with Kloosterman sums, and prove an extension for correlation sums of Kloosterman sums against Fourier coefficients of modular forms. We use these bounds to improve on earlier results on sums of Kloosterman sums along the primes and on the error term of the fourth moment of Dirichlet L-functions.