Thermoanalytical study of acetylacetonate-modified titanium(IV) isopropoxide as a precursor for TiO<Subscript>2</Subscript> films

Thermal decomposition of dried TiO₂ gel, obtained by hydrolysing acetylacetonate-modified titanium(IV) isopropoxide, was monitored by simultaneous TG/DTA/EGA-FTIR measurements in dynamic air up to 900&deg;C. XRD and FTIR were employed to identify the solid reaction products. Thermal degradation of the TiO₂ gel consists of five distinct mass loss steps, the total mass loss being 43.8&percnt;. EGA by FTIR revealed the release of H₂O below 120&deg;C; followed by acetone, isopropyl acetate and 1-propanol around 200-300&deg;C, and finally CO and CO₂ up to 550&deg;C. Highly exothermic reaction at 410-550&deg;C is caused by the combustion of carbon residues. Crystalline TiO₂-anatase is formed around 500&deg;C and TiO₂-rutile close to 800&deg;C.     

Alnumycins A2 and A3: new inverse-epimeric pairs stereoisomeric to alnumycin A1

Two new pairs of stereoisomeric alnumycin As, A2 {(2)-(1R,1′RS,4′SR,5′SR)} and A3 {(2)-(1R,1′RS,4′SR,5′RS)}, are described. Similar to alnumycin A1 {(2)-(1R,1′RS,4′RS,5′SR)}, each of these naturally occurring compounds is also a pair of C-1 inverse epimers. The relative configurations of the dioxane ring sidechains were assigned on the basis of ¹H NMR NOE contacts and molecular modeling using density functional theory (DFT) at the M06-2X/6-31G(d) level of theory. The absolute configurations of C-1 and the determination of inverse epimeric relationships were achieved by experimental electronic circular dichroism (ECD) measurements, with both aspects confirmed by using the chiral derivatizing agent (CDA) Mosher′s acid chloride {α-methoxy-α-trifluorophenylacetyl chloride (MTPACl)} to effect enantiodifferentiation. The absolute configurations of the dioxane ring using the CDA could only be effected in the case of alnumycin A1, the results of which were in agreement with previous assignments. The dioxane ring conformational mobility and the likely interaction between the MTPA groups coupled with the structural novelty of the diols in the dioxane ring with respect to CDA analysis precluded an absolute configuration assignment for alnumycins A2 and A3 based on empirical comparisons or by computational analysis of through-space NMR shieldings (TSNMRS) emanating from the phenyl groups of the MTPA moieties.     

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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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.