Synthesis of Amides and Esters by Palladium(0)-Catalyzed Carbonylative C(sp3)−H Activation

The 1,4-palladium shift strategy allows the functionalization of remote C−H bonds that are difficult to reach directly. Reported here is a domino reaction proceeding by C(sp³)−H activation, 1,4-palladium shift, and amino- or alkoxycarbonylation, which generates a variety of amides and esters bearing a quaternary β-carbon atom. Mechanistic studies showed that the aminocarbonylation of the σ-alkylpalladium intermediate arising from the palladium shift is fast using PPh₃ as the ligand, and leads to the amide rather than the previously reported indanone product.     

Sensitive CE-MS method for monitoring of riociguat and desmethylriociguat levels in human serum

Riociguat is novel antihypertensive drug for treatment of pulmonary hypertension. As such, it is still being tested in many clinical and pharmacokinetic trials. Existing methods that determine serum riociguat and desmethylriociguat (DMR) are based solely on liquid chromatography with mass spectrometry. Therefore, we present a novel capillary electrophoresis with mass spectrometry method (CE-MS) for their determination in human serum as alternative method for ongoing trials. Complete resolution of both analytes was achieved by means of pH optimization of ammonium formate background electrolytes that are fully compatible with ESI/MS detection. Simple liquid-liquid extraction was used as sample pretreatment. The calibration dependence of the method was linear (in the range of 10–1000 ng/mL), with adequate accuracy (90.1–114.9%) and precision (13.4%). LOD and LOQ were arbitrarily set at 10 ng/mL for both analytes. Clinical applicability was validated using serum samples from patients treated with riociguat in pharmacokinetic study and the results corresponded with reference HPLC-MS/MS values. Capillary electrophoresis proved to be sensitive and selective tool for the analysis of riociguat and DMR.     

Sublimation Properties of α,ω-Diamines Revisited from First-Principles Calculations

Sublimation enthalpies of alkane-α,ω-diamines exhibit an odd-even pattern within their homologous series. First-principles calculations coupled with the quasi-harmonic approximation for crystals and with the conformation mixing model for the ideal gas are used to explain this phenomenon from the theoretical point of view. Crystals of the odd and even alkane-α,ω-diamines distinctly differ in their packing motifs. However, first-principles calculations indicate that it is a delicate interplay of the cohesive forces, phonons, molecular vibrations and conformational equilibrium which governs the odd-even pattern of the sublimation enthalpies within the homologous series. High molecular flexibility of the alkane-α,ω-diamines predetermines higher sensitivity of the computational model to the quality of the optimized geometries and relative conformational energies. Performance of high-throughput computational methods, such as the density functional tight binding (DFTB, GFN2-xTB) and the explicitly correlated dispersion-corrected Møller - Plesset perturbative method (MP2C-F12), are benchmarked against the consistent state-of-the-art calculations of conformational energies and interaction energies, respectively.     

Space charge limited electric currents in thin-film metal-InSb-metal structures

The VA characteristics of thin-film metal-InSb-metal structures are analyzed in the temperature interval from –100 °C to 140 °C, up to an electric field intensity ofE 2×10⁴ V/cm, on samples having an InSb resistivity of 10⁴ cm, and prepared by cathodic sputtering. In interpreting the VA characteristics, we start out from Lampert's theory on space charged limited electric currents, according to which the injection of carriers of one kind is considered and the mobility of the carriers depends upon the electric field intensity. Attention is drawn to the qualitative agreement of the experimental and theoretical results.     

Über die an „Schwachen“ Grenzflächen Entstehenden Kopfwellen

Zusammenfassung In der vorliegenden Arbeit werden die Kopfwellen untersucht, die beim Auffallen einer harmonischen Schall-Kugelwelle auf die Ebene Grenzfläche zwischen zwei flüssigen Medien entstehen. Vorausgesetzt wird, daß die Grenzfläche schwach ist, d. h. daß die Geschwindigkeit der Schallwellen im Medium mit der Erregungsquelle nur um weniges kleiner ist als die Geschwindigkeit der Schallwellen im Medium ohne die Quelle.

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Luminescence due to the disintegration of transient colour centres in YAG : Nd single crystals

Luminescence accompanying the disintegration of colour centres formed by the intensive irradiation of the YAG : Nd single crystals with light containing near UV region of the spectrum is studied. Spectral distribution is studied together with the luminescence decay kinetics.     

On Properties of Rectangular Hyperbolas

This paper improves an old theorem about a rectangular hyperbola : its centre lies on the pedal circle of any point on with respect to any triangle inscribed in . We also prove that an analogous result holds for Cevian circles. These results are used to obtain new characterisations of the Feuerbach, Jarabek, and Kiepert hyperbolas of a triangle.     

Topology and geometry of nematic braids

Topological analysis of disclinations in nematic liquid crystals is an interesting and diverse topic that goes from strict mathematical theorems to applications in elaborate systems found in experiments and numerical simulations. The theory of nematic disclinations is shown from both the geometric and topological perspectives. Entangled disclination line networks are analyzed based on their shape and the behavior of their cross section. Methods of differential geometry are applied to derive topological results from reduced geometric information. For nematic braids, systems of −1/2 disclination loops, created by inclusion of homeotropic colloidal particles, a formalism of rewiring is constructed, allowing comparison and construction of an entire set of different conformations. The disclination lines are described as ribbons and a new topological invariant, the self-linking number, is introduced. The analysis is generalized from a constant −1/2 profile to general profile variations, while retaining the geometric treatment. The workings of presented topological statements are demonstrated on simple models of entangled nematic colloids, estimating the margins of theoretical assumptions made in the formal derivations, and reviewing the behavior of the disclinations not only under topological, but also under free-energy driven constraints.