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).     

Far-infrared detector based on HgTe/HgCdTe superlattices

HgTe/Hg_0.05Cd_0.95Te superlattices (SLs) were grown on (112)B oriented Cd_0.96Zn_0.04 Te substrates using molecular beam epitaxy (MBE). The SLs, consisting of 100 periods of 80-Å-thick HgTe wells alternating with 77-Å-thick Hg_0.05Cd_0.95Te barriers, were designed to operate as detectors in the far-infrared (FIR) region. Infrared absorption spectroscopy, high-resolution transmission electron microscopy (TEM), Hall effect measurements, and x-ray diffraction were used to characterize the superlattice layers. A series of annealing experiments were initiated to quantify the temperature-dependent interdiffusion of the HgTe wells and Hg_0.05Cd_0.95Te barriers and consequently their degradation, which shifts the absorption edges of the SLs to higher energies, since a high-temperature ex situ anneal is normally required in order to produce the p-type material required for a photovoltaic detector. Results from infrared absorption spectroscopy, TEM, and Hall effect measurements for the annealed samples are presented. A FIR SLs single-element photoconductive (PC) device was designed and fabricated. Both material characterization and device testing have established the applicability of the HgTe/Hg_0.05Cd_0.95Te SLs for the FIR region.     

Multiple Scan Chain Design for Two-Pattern Testing

Non-standard fault models often require the application of two-pattern testing. A fully-automated approach for generating a multiple scan chain-based architecture is presented so that two-pattern test sets generated for the combinational core can be applied to the sequential circuit. Test time and area overhead constraints are considered.     

Ultra-low-energy ion-beam-synthesis of Ge nanocrystals in thin ALD Al2O3 layers for memory applications

Structural and electrical properties of ALD-grown 5 and 7 nm-thick Al₂O₃ layers before and after implantation of Ge ions (1 keV, 0.5–1 × 10¹⁶ cm^?2) and thermal annealing at temperatures in the 700–1050 °C range are reported. Transmission Electron Microscopy reveals the development of a 1 nm-thick SiO₂-rich layer at the Al₂O₃/Si substrate interface as well as the formation of Ge nanocrystals with a mean diameter of ～5 nm inside the implanted Al₂O₃ layers after annealing at 800 °C for 20 min. Electrical measurements performed on metal–insulator–semiconductor capacitors using Ge-implanted and annealed Al₂O₃ layers reveal charge storage at low-electric fields mainly due to location of the Ge nanocrystals at a tunnelling distance from the substrate and their spatial dispersion inside the Al₂O₃ layers.     

Concentration-dependent 4I13/2 lifetimes inEr3+-doped fibers and Er3+-doped planar waveguides

We report on the concentration- and pump-dependent lifetimes of the spontaneous emission in Er³⁺-doped fibers and Er³⁺ -doped waveguides. In addition, we measure the concentration dependence of the 550-nm fluorescence due to excited state absorption (ESA)     

Investigation of iodine as a donor in MBE grown Hg1−xCdxTe

N-type Hg_1−xCd_xTe layers with x values of 0.3 and 0.7 have been grown by molecular beam epitaxy using iodine in the form of CdI₂ as a dopant. Carrier concentrations up to 1.1 × 10¹⁸ cm⁻³ have been achieved for x = 0.7 and up to 7.6 × 10¹⁷ cm⁻³ for x=0.3. The best low temperature mobilities are 460 cm²/(Vs) and 1.2 × 10⁵ cm²/(Vs) for x=0.7 and x=0.3, respectively. Using CdI₂ as the dopant modulation doped HgTe quantum well structures have been grown. These structures display very pronounced Shubnikov-de Haas oscillations and quantum Hall plateaus. Electron densities in the 2D electron gas in the HgTe quantum well could be varied from 1.9 × 10¹¹ cm⁻² up to 1.4 × 10¹² cm⁻² by adjusting the thicknesses of the spacer and doped layer. Typical mobilities of the 2D electron gas are of the order of 5.0 × 10⁴ cm²/(Vs) with the highest value being 7.8 × 10⁴ cm²/(Vs).     

Performance of a high concentration Er/sup 3+/-doped alumino silicate fiber amplifier

We report the gain, noise figure, output saturation power, and conversion efficiency of a highly concentrated Er/sup 3+/-doped alumino silicate fiber amplifier. We obtain a gain per unit length of 1.0 dB/cm, which corresponds to the highest gain per unit length obtained in an Er/sup 3+/-doped fiber amplifier. The pump power threshold ranges from 2 to 5 mW, depending on the fiber length.