Kinetik und Mechanismus der Photolyse von Aryldiazoniumsalzen in Methanol. Ermittlung absoluter Geschwindigkeitskonstanten einiger Teilreaktionen

Kinetics and Mechanism of Aryldiazonium Salt Photolysis in Methanol. Determination of Absolute Rate Constants of Some Reaction Steps For benzene diazonium tetrafluoroborate and some p-substituted derivatives, the following values are determined:

• velocity constants for the photochemical electron transfer from pyrene and benzanthracene to aryl diazonium salts in acetonitrile solution (determination by quenching the donor fluorescence).
• velocity constants for electron transfer under the condition of pulse radiolysis in tert.-butanol-water solution;
• quantum yields and product composition (ArOMe, ArF and ArH, respectively) for the photolyses in methanol in the presence of varying concentrations of 2-methyl-2-nitroso-propane as a quencher of the thermal chain reaction.

The electron transfer reaction comes out be a diffusion controlled reaction, k_E = 2 …︁ 3 × 10¹⁰ M⁻¹ s⁻¹. For the total reaction a kinetic model is set up which affords absolute velocity constants from the experimental results for the following steps: Hydrogen transfer within the case radical pair \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {{\rm Ar} - {\rm N} = {\rm N}{\rm . CH}_{\rm 3} {\rm OH}{\rm .}} {\rm }^ \oplus $\end{document} (formation of ArH) k_H ≈ 10¹¹ s⁻¹; Maximal values for the photo-solvolyses (formation of Ar^⊕ → ArOMe and ArF, respectively), k_s ≲ 10⁻¹; Trapping of aryl radicals outside of the solvent cage by t-BuNO, k_q ≈ 2 × 10⁷ M⁻¹ s⁻¹. The results are discussed in the light of the kinetic model and some other facts.     

SARS-CoV-2 Infection Dysregulates Cilia and Basal Cell Homeostasis in the Respiratory Epithelium of Hamsters

Similar to many other respiratory viruses, SARS-CoV-2 targets the ciliated cells of the respiratory epithelium and compromises mucociliary clearance, thereby facilitating spread to the lungs and paving the way for secondary infections. A detailed understanding of mechanism involved in ciliary loss and subsequent regeneration is crucial to assess the possible long-term consequences of COVID-19. The aim of this study was to characterize the sequence of histological and ultrastructural changes observed in the ciliated epithelium during and after SARS-CoV-2 infection in the golden Syrian hamster model. We show that acute infection induces a severe, transient loss of cilia, which is, at least in part, caused by cilia internalization. Internalized cilia colocalize with membrane invaginations, facilitating virus entry into the cell. Infection also results in a progressive decline in cells expressing the regulator of ciliogenesis FOXJ1, which persists beyond virus clearance and the termination of inflammatory changes. Ciliary loss triggers the mobilization of p73⁺ and CK14⁺ basal cells, which ceases after regeneration of the cilia. Although ciliation is restored after two weeks despite the lack of FOXJ1, an increased frequency of cilia with ultrastructural alterations indicative of secondary ciliary dyskinesia is observed. In summary, the work provides new insights into SARS-CoV-2 pathogenesis and expands our understanding of virally induced damage to defense mechanisms in the conducting airways.     

Steric Crowding Makes Challenging C(sp3)-F Reductive Eliminations Feasible

A high-yielding fluorination of (triphos)Pt-R(+) has been achieved using an array of F(+) sources, with XeF(2) yielding R-F in minutes. The C-F coupling proved to be a stereoretentive process that proceeds via a concerted reductive elimination from a putative dicationic Pt(IV) center. The larger the steric congestion of the (triphos)Pt-C(sp3) (+) complexes, the more efficient the fluorination, seemingly a result of sterically accelerated C-F reductive elimination along with simultaneous deceleration of its competing processes (β-H elimination).     

A comparison of two sampling methods for global sensitivity analysis

We compare the convergence properties of two different quasi-random sampling designs – Sobol?s quasi-Monte Carlo, and Latin supercube sampling in variance-based global sensitivity analysis. We use the non-monotonic V-function of Sobol? as base case-study, and compare the performance of both sampling strategies at increasing sample size and dimensionality against analytical values. The results indicate that in almost all cases investigated here, the Sobol? design performs better. This, coupled with the fact that effective Latin supercube sampling requires a priori knowledge of the interaction properties of the function, leads us to recommend Sobol? sampling in most practical cases.     

Fortschritte in der Verminderung der Umweltbelastung bei der Herstellung von gebleichten Sulfatzellstoffen

The sulphate process became worldwide the most important pulping process. Sulphate pulps possess higher strength properties than sulphite pulps. Moreover, any wood species can be pulped according to the sulphate method. Pollution problems are the main impediment to some countries to use this pulping technique. In the article the different emission sources due to sulphate pulping are discussed and the various ways of their reduction, are described. Modern bleaching techniques for sulphate pulps such as oxygen prebleaching, alkaline extraction in presence of oxygen or hydrogen peroxyde and the use of chlorone dioxide as a bleaching agent are the main methods to reduce pollution. Also extended pulping decreses the, bleach requirement. The importance of sulphate pulping for wood utilization in the Federal Republic of Germany is briefly discussed.