Voltammetric and titrimetric study of acid-base properties of some μ-oxo dimeric iron(III) complexes inDMF

Summary The acid-base properties of the -oxo bridged dimeric iron complexes [FeL]₂O with the ligands based on S-alkyl-1,4-bis(substituted salicylidene)isothiosemicarbazide and a tetramer with S-methyl-1,4-bis(salicylidene)isothiosemicarbazide, {[FeL]₂O}₂I₃·I₂, were investigated by cyclic voltammetry at glassy carbon electrode inDMF. Studies were carried out in the presence of either a weak (phenol) or a strong (HClO₄ aq.) acid. The stoichimoetry of the reaction, changes in the general voltammetric pattern and the electrode reaction mechanism were discussed. These studies served as the basis for three-electrode amperometric titrations to determine the content of several of these complexes.

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Voltammetrische und titrimetrische Untersuchung der Säure-Base-Eigenschaften einiger -oxo dimerer Eisen(III)-Komplexe inDMF-Lösungen

Zusammenfassung Die Säure-Base-Eigenschaften einiger dimerer -oxo-Eisen(III)-Komplexe [FeL]₂O mit Liganden auf Basis von 1,4-bis(substituierten Salicyliden)S-(alkyl)isothiosemicarbaziden sowie eines tetrameren Komplexes mit 1,4-Bis(salicyliden)S-methylisothiosemicarbazid, {[FeL]₂O}₂I₃·I₂, wurden mittels zyklischer Voltammetrie an der Glaskohlenstoffelektrode inDMF-Lösungen untersucht. Die Messungen wurden in Gegenwart entweder einer schwachen (Phenol) oder einer starken (HClO₄ aq.) Säure ausgeführt. Die Stöchiometrie der Reaktion, die Änderungen der voltammetrischen Kurven und der Elektroden-Reaktionsmechanismus wurden diskutiert. Diese Untersuchungen stellten eine Basis für Drei-Elektroden amperometrische Titrationen dar, die für die Bestimmung des Gehalts einiger dieser Komplexe angewendet wurden.

     

High pressure lattice dynamics, dielectric and thermodynamic properties of SrO

Using density functional theory and density functional perturbation theory we have studied the effects of hydrostatic pressure on lattice dynamics, dielectric and thermodynamic properties of the rocksalt (NaCl) and CsCl phases of SrO. The stability of the NiAs type structure, experimentally confirmed to be stable in BaO, is also investigated. Studying the lattice dynamics of the NaCl and CsCl phases at various pressures, in the range of the phase stability, we have found the lattice dynamical instabilities which govern the phase transitions between NaCl and CsCl phases with increasing and decreasing pressure. By monitoring the behaviour of the found soft modes, we have calculated the transition pressures upon compression and decompression of SrO crystal. Lattice dynamics calculations reveal that the rocksalt and CsCl structures are unstable with respect to the soft transversal acoustic modes at single points of the Brillouin zone, which points to the fact that the transitions are of displacive type. Responses to electric fields and thermodynamic properties at high pressures are also given and discussed. All our results are in a good agreement with experimental data where applicable.     

Superelectrophilic amidine dications: dealkylation by triflate anion

Superelectrophiles: Formamides were designed that when treated with triflic anhydride would be transformed into superelectrophilic amidine dications. These dications were so electrophilic that they underwent in?situ dealkylation by the triflate anion (see scheme; Tf=trifluoromethanesulfonyl). DFT calculations were used to determine the mechanistic details of the dealkylation reaction.     

Localized end states in density modulated quantum wires and rings

We study finite quantum wires and rings in the presence of a charge-density wave gap induced by a periodic modulation of the chemical potential. We show that the Tamm-Shockley bound states emerging at the ends of the wire are stable against weak disorder and interactions, for discrete open chains and for continuum systems. The low-energy physics can be mapped onto the Jackiw-Rebbi equations describing massive Dirac fermions and bound end states. We treat interactions via the continuum model and show that they increase the charge gap and further localize the end states. The electrons placed in the two localized states on the opposite ends of the wire can interact via exchange interactions and this setup can be used as a double quantum dot hosting spin qubits. The existence of these states could be experimentally detected through the presence of an unusual 4π Aharonov-Bohm periodicity in the spectrum and persistent current as a function of the external flux.     

Structural and Functional Analysis of Bacterial Sulfonosphingolipids and Rosette-Inducing Factor 2 (RIF-2) by Mass Spectrometry-Guided Isolation and Total Synthesis

We have analyzed the abundance of bacterial sulfonosphingolipids, including rosette-inducing factors (RIFs), in seven bacterial prey strains by using high-resolution tandem mass spectrometry (HRMS²) and molecular networking (MN) within the Global Natural Product Social Molecular Networking (GNPS) web platform. Six sulfonosphingolipids resembling RIFs were isolated and their structures were elucidated based on comparative MS and NMR studies. Here, we also report the first total synthesis of two RIF-2 diastereomers and one congener in 15 and eight synthetic steps, respectively. For the total synthesis of RIF-2 congeners, we employed a decarboxylative cross-coupling reaction to synthesize the necessary branched α-hydroxy fatty acids, and the Garner-aldehyde approach to generate the capnine base carrying three stereogenic centers. Bioactivity studies in the choanoflagellate Salpingoeca rosetta revealed that the rosette inducing activity of RIFs is inhibited dose dependently by the co-occurring sulfonosphingolipid sulfobacins D and F and that activity of RIFs is specific for isolates obtained from Algoriphagus.     

Mechanoluminescence induced by elastic and plastic deformation of coloured alkali halide crystals at fixed strain rates

Mechanoluminescence (ML) emission from coloured alkali halide crystals takes place during their elastic and plastic deformation. The ML emission during the elastic deformation occurs due to the mechanical interaction between dislocation segments and F-centres, and the ML emission during the plastic deformation takes place due to the mechanical interaction between the moving dislocations and F-centres. In the elastic region, the ML intensity increases linearly with the strain or deformation time, and in this case, the saturation region could not be observed because of the beginning of the plastic deformation before the start of the saturation in the ML intensity. In the plastic region, initially the ML intensity also increases linearly with the strain or deformation time, and later on, it attains a saturation value for large deformation. When the deformation is stopped, initially the ML intensity decreases at a fast rate; later on, it decreases at a slow rate. The decay time for the fast decrease of the ML intensity gives the relaxation time of dislocation segments or pinning time of the dislocations, and the decay time of the slow decrease of the ML intensity gives the diffusion time of holes in the crystals. The saturation value of the ML intensity increases linearly with the strain rate and also with the density of F-centres in the crystals. Initially, the saturation value of the ML intensity increases with increasing temperature, and for higher temperatures the ML intensity decreases with increasing temperature. Therefore, the ML intensity is optimum for a particular temperature of the crystals. From the ML measurements, the relaxation time of dislocation segments, pinning time of dislocations, diffusion time of holes and the energy gap between the bottom of the acceptor dislocation band and interacting F-centre level can be determined. Expressions derived for the ML induced by elastic and plastic deformation of coloured alkali halide crystals at fixed strain rates indicates that the ML intensity depends on the strain, strain rate, density of colour centres, size of crystals, temperature, luminescence efficiency, etc. A good agreement is found between the theoretical and experimental results.     

Anodic Stripping Voltammetry Combined with Sequential Injection Analysis for Measurements of Trace Metal Ions with Bismuth‐ and Antimony Film Electrodes under Comparable Conditions

Anodic stripping voltammetry combined with sequential injection analysis (ASV‐SIA) was selected to examine the use of bismuth‐ and antimony‐film plated glassy carbon electrodes under comparable conditions for the determination of Pb(II) and Cd(II) ions. Of interest were the conditions for film deposition, as well as the composition of sample/carrier solutions, including concentrations of Sb(III) or Bi(III) and HCl. Then, by the optimized procedure, one could determine Pb(II), Cd(II), and Zn(II) ions at the low µg L^?1 level and ASV‐SIA configuration with both electrodes tested on analysis of a water sample.     

Microstructural identification of Cu in solar cells sensitive to light‐induced degradation

Light‐induced degradation (mc‐LID or LeTID) can lead to a severe efficiency loss in multi‐crystalline solar cells. The underlying mechanism clearly distinguishes from known mechanisms as B‐O‐LID and Fe‐B‐LID. Various defect models have been suggested for mc‐LID mainly based on metal impurities, including Cu which is known to cause light‐induced degradation. We investigate mc‐LID sensitive PERC cells that show an efficiency degradation of 15%_rel. The weaker degradation of the grain boundaries (GBs) typical for mc‐LID is identified and further investigated from front and rear side with respect to recombination activities. The combination of local electrical measurements (LBIC), target preparation (REM, FIB) and element analysis (EDX, TEM) unveil Cu‐containing precipitates at the rear side of the solar cells. They accumulate at grain boundaries and at the rear surface of the Si‐bulk material where the passivation stack is damaged. We conclude that Cu originates from the cell material and discuss its relation to mc‐LID.

LBIC mapping (EQE at fixed wavelength) of a degraded mc‐Si PERC cell from front and rear side results in qualitatively different appearance of GBs.     

Dispelling myths on superposition attacks: formal security model and attack analyses

Designs, Codes and Cryptography - With the emergence of quantum communication, it is of folkloric belief that the security of classical cryptographic protocols is automatically broken if the...