Gas-Phase Lithium Cation Basicity: Revisiting the High Basicity Range by Experiment and Theory

According to high level calculations, the upper part of the previously published FT-ICR lithium cation basicity (LiCB at 373 K) scale appeared to be biased by a systematic downward shift. The purpose of this work was to determine the source of this systematic difference. New experimental LiCB values at 373 K have been measured for 31 ligands by proton-transfer equilibrium techniques, ranging from tetrahydrofuran (137.2 kJ mol^?1) to 1,2-dimethoxyethane (202.7 kJ mol^?1). The relative basicities (ΔLiCB) were included in a single self-consistent ladder anchored to the absolute LiCB value of pyridine (146.7 kJ mol^?1). This new LiCB scale exhibits a good agreement with theoretical values obtained at G2(MP2) level. By means of kinetic modeling, it was also shown that equilibrium measurements can be performed in spite of the formation of Li⁺ bound dimers. The key feature for achieving accurate equilibrium measurements is the ion trapping time. The potential causes of discrepancies between the new data and previous experimental measurements were analyzed. It was concluded that the disagreement essentially finds its origin in the estimation of temperature and the calibration of Cook’s kinetic method. Graphical Abstract

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Bromine formation in solid NaBr/KNO<Subscript>3</Subscript> mixture and assay of this reaction via bromination of activated aromatics

Bromine formation in the mixture of solid NaBr and KNO₃ was observed and the process was studied in different acidified organic solvent–water mixtures by monitoring the bromination of acetanilide and other compounds, containing activated aromatic substituents. This assay is based on fast bromination reaction of these aromatic compounds, as differently from the assay of Br₂, the brominated aromatics can be easily determined by conventional gas chromatography–mass spectrometry (GC–MS) methods. It was found that bromine was generated autocatalytically on the surface of salt crystals and the reaction was characterized by a lag period, the duration of which depended on reaction conditions, and importantly on the type of the organic solvent in the reaction mixture. As the bromine formation could be easily controlled by reaction conditions, it was suggested that the studied reaction might have practical applications as an environmentally friendly and economically feasible bromination method. It was also shown that the bromination of aromatics followed the mechanism of classical electrophilic aromatic substitution reaction.     

Femoral head avascular necrosis in sickle cell anemia: MR characteristics

Since considerable expansion of hematopoietic marrow occurs in patients with sickle cell anemia (SCA), magnetic resonance images of 20 hips in 10 patients with known homozygous SCA were reviewed to determine a) if low signal hematopoietic marrow extended into the femoral capital epiphysis and b) if the MR characteristics of avascular necrosis (AVN) differed depending on the type of epiphyseal marrow. Our results revealed variable epiphyseal marrow type; mixed (fatty and hematopoietic) marrow (42%), fatty marrow (32%), hematopoietic marrow (16%) and hemosiderotic marrow (10%). AVN occurred irrespective of the underlying marrow. Segmental areas of low signal intensity in variable shapes (ring, band, crescent or large homogeneous area) was the most consistent MR manifestation of AVN in SCA. A low signal intensity peripheral rim surrounding a central zone, isointense with epiphyseal marrow on T₁ and T₂ weighted images, was most frequently observed similar to that described in patients without hemoglobinopathy. The notable difference, however, was of segmental areas within the same femoral head that demonstrated variable central zone signal on T₂ weighted images. Further, while an increase in hip joint fluid is commonly seen with both early and advanced AVN in patients without hemoglobinopathy; it was increased in only one hip in patients with SCA. The observed differences in MR characteristics may be due to different pathophysiology of AVN in patients with SCA.     

Effect of frequency on sonochemical reactions. I: Oxidation of iodide

The effect of continuous sonication on the kinetics of iodine formation in aqueous iodide solutions was studied in the presence of air and argon at two frequencies, 20 and 900 kHz. Most workers in this area assume that frequency has a negligible effect on sonochemical reactions. The present results indicate, however, that there is a significant effect in the above solutions. The rate of sonochemical oxidation of iodide in aqueous solution is 3.1 times greater in presence of air than argon at 900 kHz, in contrast to the situation at 20 kHz, where the ratio is 0.9 A 900 kHz apparatus was specially designed to make it possible to measure the absolute acoustic power delivered into the solution. The rate of oxidation per unit power in this new 900 kHz apparatus can be more than 30 times greater than that at 20 kHz for the oxidation of iodide in the presence of air.     

D'Alembert's letter to Euler of 3 march 1766

Just before Leonhard Euler resigned his post at the Berlin Academy to return to St. Petersburg, where he spent the rest of his life, he received a letter from d'Alembert urging him to remain in Berlin. This letter is here published for the first time with commentary on the historical context.     

Selective inclusion of cesium ion in a cryptand-type Ti(IV) complex derived from a tripodal tris-2,3-dihydroxynaphthalene ligand

A novel tripodand-type ligand (L1) having three 2,3-dihydroxynaphthalene end groups and a C₃ symmetric 1,3,5-tryimethylbenzene based backbone was prepared by the reaction of 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene with 3-(2-(hydroxymethyl)allyloxy)naphthalene-2-ol followed by triple Claisen rearrangement. A 1:1 titanium complex which acts as a metallo-cryptand is obtained by the reaction of ligand (L1) with Ti(IV)(=O)(acac)₂ in the presence of base. The formation of the metallo-cryptand strongly depends on templating effects by counter cations and it shows a high selectively for the encapsulation of cesium cations in its cavity.