Synthesis,structure and catalytic properties of bis[2‐(trifluoromethyl)phenyl]silanediol

A novel trifluoromethylaryl‐substituted disilanol, bis[(2‐trifluoromethyl)phenyl] silanediol, was prepared by hydrolysis of the precursor dichloride and fully characterized. Single‐crystal X‐ray diffraction indicates doubly linked hydrogen bonded dimers and also hydrogen bonding to tetrahydrofuran solvent. The acidity of the silanol functions is enhanced by the presence of the trifluoromethyl groups and the compound is found to be active in promoting a standard Diels–Alder reaction, increasing yields by a factor of three.     

Lie algebra type noncommutative phase spaces are Hopf algebroids

For a noncommutative configuration space whose coordinate algebra is the universal enveloping algebra of a finite-dimensional Lie algebra, it is known how to introduce an extension playing the role of the corresponding noncommutative phase space, namely by adding the commuting deformed derivatives in a consistent and nontrivial way; therefore, obtaining certain deformed Heisenberg algebra. This algebra has been studied in physical contexts, mainly in the case of the kappa-Minkowski space-time. Here, we equip the entire phase space algebra with a coproduct, so that it becomes an instance of a completed variant of a Hopf algebroid over a noncommutative base, where the base is the enveloping algebra.     

Elucidation of the Reaction Products of Acetonitrile with Phosphorus Pentachloride

Abstract

The reaction of acetonitrile with PCl, results in the ionic compounds (1) to (4) containing the trichloro[2-chloro-2-[(trichlorophosphoranyli-dene)amino]ethenyl]phosphorus cations and not in the compounds [CH2?C?NPCl₃]PCl₆1 or trichloro[2-chloro-1 -[(trichlorophosphoranyli-dene)amino] ethenyl]phosphorus hexachlorophosphate (5) as assumed from ³¹P-NMR spectra [2, 3]. The crystal structures of the compounds (1) to (4) were determined with X-rays at 95K. As observed for the CI-C(NPCl₃); cation all the cations show cis-trans conformations with respect to their CI-C-X-P torsion angles. The wcl3 groups of the cations have two different orientations with one C?N?P?CI torsion angle of about 0° (cis) as in (1) or about 180° (trans) as in (3) and (4). In the salt (2) there are two formula units in the asymmetric unit with one cation showing the cis and the other showing the tram conformation.     

Solubilisation of camptothecin by nonionic surfactants and alkyldimethylamine oxides

The solubilisation of poorly soluble antineoplastic drug camptothecin by nonionic surfactants (polysorbates and octylphenol ethoxylates) and alkyldimethylamine oxide surfactants with the alkyl chain length 8 to 16 carbon atoms was investigated. The hydrophobicity of the solubilising agent turned out to be the primary structural parameter controlling the solubility efficiency of camptothecin in an aqueous solution. The quantitative parameter of solubilisation (drug loading coefficient) provided values in the range of 0.1–1.2% and 0.1–1.0% for alkyldimethylamine oxides and nonionic surfactants, respectively. The decreasing number of oxyethylene units and the extension of the hydrophobic part of nonionic surfactant molecule resulted in the increase of camptothecin solubility. From the dynamic light scattering measurements, the hydrodynamic diameter values of camptothecin-loaded alkyldimethylamine oxide and nonionic micelles were found in the range of 4–42 nm and 5–120 nm, respectively. The experimental values confirmed the increase in micellar size with the increasing alkyl chain length. The values of the packing parameter of camptothecin-loaded dodecyldimethylamine oxide micelles indicate their spherical shape at all the investigated surfactant concentrations. A simple computer model of camptothecin-loaded dodecyldimethylamine oxide micelle provided the diameter of the structure cross section which is consistent with the experimental values.      

Fast concentration of dissolved forms of cesium radioisotopes from large seawater samples

The method developed for cesium concentration from large freshwater samples was tested and adapted for analysis of cesium radionuclides in seawater. Concentration of dissolved forms of cesium in large seawater samples (about 100 L) was performed using composite absorbers AMP-PAN and KNiFC-PAN with ammonium molybdophosphate and potassium–nickel hexacyanoferrate(II) as active components, respectively, and polyacrylonitrile as a binding polymer. A specially designed chromatography column with bed volume (BV) 25 mL allowed fast flow rates of seawater (up to 1,200 BV h^?1). The recovery yields were determined by ICP-MS analysis of stable cesium added to seawater sample. Both absorbers proved usability for cesium concentration from large seawater samples. KNiFC-PAN material was slightly more effective in cesium concentration from acidified seawater (recovery yield around 93 % for 700 BV h^?1). This material showed similar efficiency in cesium concentration also from natural seawater. The activity concentrations of ¹³⁷Cs determined in seawater from the central Pacific Ocean were 1.5 ± 0.1 and 1.4 ± 0.1 Bq m^?3 for an offshore (January 2012) and a coastal (February 2012) locality, respectively, ¹³⁴Cs activities were below detection limit (<0.2 Bq m^?3).     

Enantioselective Michael additions of aldehydes to nitroalkenes catalyzed with ionically tagged organocatalyst

Enantioselective organocatalytic Michael additions affords useful building blocks for many biologically and medicinally relevant compounds. Ionically-tagged diphenylprolinol silyl ether efficiently catalyzes several Michael additions of aldehydes to nitroalkenes in ionic liquids. The Michael additions work well in ionic liquids; yields up to 95% and enantioselectivities up to 95% ee were achieved. Furthermore, in some cases, the catalytic system was reusable.