Series of mixed uranyl-lanthanide (ce, nd) organic coordination polymers with aromatic polycarboxylates linkers

Three series of mixed uranyl-lanthanide (Ce or Nd) carboxylate coordination polymers have been successfully synthesized by means of a hydrothermal route using either conventional or microwave heating methods. These compounds have been prepared from mixtures of uranyl nitrate, lanthanide nitrate together with phthalic acid (1,2), pyromellitic acid (3,4), or mellitic acid (5,6) in aqueous solution. The X-ray diffraction (XRD) single-crystal revealed that the phthalate complex (UO(2))(4)O(2)Ln(H(2)O)(7)(1,2-bdc)(4)·NH(4)·xH(2)O (Ln = Ce(1), Nd(2); x = 1 for 1, x = 0 for 2), is based on the connection of tetranuclear uranyl-centered building blocks linked to discrete monomeric units LnO(2)(H(2)O)(7) via the organic species to generate infinite chains, intercalated by free ammonium cations. The pyromellitate phase (UO(2))(3)Ln(2)(H(2)O)(12)(btec)(3)·5H(2)O (Ce(3), Nd(4)) contains layers of monomeric uranyl-centered hexagonal and pentagonal bipyramids linked via the carboxylate arms of the organic molecules. The three-dimensionality of the structure is ensured by the connection of remaining free carboxylate groups with isolated monomeric units LnO(2)(H(2)O)(7). The network of the third series (UO(2))(2)(OH)Ln(H(2)O)(7)(mel)·5H(2)O (Ce(5), Nd(6)) is built up from dinuclear uranyl units forming layers through connection with the mellitate ligands, which are further linked to each other through discrete monomers LnO(3)(H(2)O)(6). The thermal decomposition of the various coordination complexes led to the formation of mixed uranium-lanthanide oxide, with the fluorite-type structure at 1500 °C (for 1, 2) or 1400 °C for 3-6. Expected U/Ln ratio from the crystal structures were observed for compounds 1-6.     

Time-resolved velocity and concentration measurements in variable-viscosity turbulent jet flow

This paper addresses the ability to reliably measure the fluctuating velocity field in variable-viscosity flows (herein, a propane–air mixture), using hot-wire anemometry. Because the latter is sensitive to both velocity and concentration fluctuations, the instantaneous concentration field also needs to be inferred experimentally. To overcome this difficulty, we show that the hot-wire response becomes insensitive to the concentration of the field, when a small amount of neon is added to the air. In this way, velocity measurements can be made independently of the concentration field. Although not necessary to velocity measurements, Rayleigh light-scattering technique is also used to infer the local (fluctuating) concentration, and, therefore, the viscosity of the fluid. Velocity and concentration measurements are performed in a turbulent propane jet discharging into an air–neon co-flow, for which the density and viscosity ratios are 1.52 and 1/5.5, respectively. The Reynolds number (based on injection diameter and velocity) is 15400. These measurements are first validated: the axial decay of the mean velocity and concentration, as well as the lateral mean and RMS profiles of velocity and concentration, is in full agreement with the existing literature. The variable-viscosity flow along the axis of the round jet is then characterized and compared with a turbulent air jet discharging into still air, for which the Reynolds number (based on injection diameter and velocity) is 5400. Both flows have the same initial jet momentum. As mixing with the viscous co-flow is enhanced with increasing downstream position, the viscosity of the fluid increases rapidly for the case of the propane jet. In comparison with the air jet, the propane jet exhibits: (1) a lower local Reynolds number based on the Taylor microscale (by a factor of four); (2) a reduced range of scales present in the flow; (3) the isotropic form of the mean energy dissipation rate is first more enhanced and then drastically diminishes and (4) a progressively increasing local Schmidt number (from 1.36 to 7.5) for increasing downstream positions. Therefore, the scalar spectra exhibit an increasingly prominent Batchelor regime with a ~ k ^?1 scaling law. The experimental technique developed herein provides a reliable method for the study of variable-viscosity flows.     

Binary adduct formation of desipramine with dicarboxylic acids

This paper presents the results obtained in a screening study for binary adduct formation of desipramine with three dicarboxylic acids—namely succinic, malonic and glutaric acids. Adduct formation is important because most tricyclic antidepressants show limited water solubility as free bases. Three binary adducts were prepared using a wet kneading method in non-homogenous media in presence of ethanol. Investigations of the solid state (ATR-FTIR, PXRD) and thermal analysis (TG/DTG/HF) were used for characterization of the prepared samples. The corroboration of data from employed instrumental techniques suggests that binary adducts in molar ratio 1:1 were obtained under the used experimental conditions.     

Synthesis, inclusion capabilities, and electrical properties of some asymmetrical cyclophanes

For the first time, we announce the synthesis of cyclo(bis-paraquat-p-phenylene-p-phenylene-carbonyl)tetrakis(hexafluorophosphate), named ‘CETOBOX’. This compound exists in three tautomeric forms. These forms were evidenced by NMR data (¹H NMR, TOCSY, COSY, and NOESY), UV-vis spectra coupled with pH measurements, and by synthesis. As the ‘CETOBOX’ gives ‘in situ’ only the corresponding monoylide, the synthesis of a new fluorescent indolizine cyclophane has been performed by a 3+2 cycloaddition. This cycloadduct, in an amidation reaction with 6-amino-β-cyclodextrin, furnishes the final two-cavity sensor with good yields. All structures of the new compounds presented herein have been established by NMR spectroscopy. Also, theoretical methods (MM3, AM1, AM1 (COSMO), and B88LYPDFT) have been used to determine the most stable conformer structures. For the fluorescent indolizine cycloadduct, we evaluated its inclusion capabilities and for the two-cavity sensor, we measured some of its electrical properties that make it suitable for use in VOCs detection and energy conversion.     

Mixed oxide growth on combinatorial aluminium–gadolinium alloys — a thermodynamic and first-principles approach

Metal surfaces covered with oxides have attracted considerable scientific attention in various applications. In particular, anodic films fabricated by cost-effective anodizing have been widely used in nano-structured engineering to provide various surface functionalities. However, understanding of alloy film stability, having individual elements with widely varying structures and morphologies, is very limited due to lack of thermodynamic information and effects of electrolyte chemistry. This requires many tedious efforts on a trial and error basis in selecting suitable electrolytes that can produce the protective film at high efficiency on alloys having mixed chemistries. It is, therefore, crucial to develop a combination of high throughput theoretical analysis and automated rapid localized electrochemical probing that provides a fast and simple solution for electrolyte choice and paves the way to the remarkable expansion of industrial applications of oxides. Herein, we demonstrate that combinatorial Al–Gd alloys covering 1.0 to 10.0 at.% Gd can be oxidized into ultra-thin anodic films of controlled thickness through a selection of electrolyte based on thermodynamics (phosphate buffer with a pH of 8.20). We propose that growth of anodic films on alloys at high efficiency is possible if Gibbs free energy minimization criteria would be systematically contemplate.

Graphical abstract

     

Metal-organic-framework-type 1D-channel open network of a tetravalent uranium trimesate

An uranium trimesate open framework is built up from trinuclear building blocks (μ(3)-OU(3)) connected to each other by tricarboxylate linkers to generate honeycomb-like 3D topology. This compound was solvothermally synthesized from low-valent uranium in an N,N-dimethylformamide solvent under an inert atmosphere, favoring stabilization of the tetravalent oxidation state, which is confirmed by X-ray photoelectron spectroscopy analysis.     

The Balassa–Samuelson effect in Romania – The role of regulated prices

Due to the Balassa–Samuelson effect, the candidate countries to the European Monetary Union face a possible conflict between the effects of tradable productivity increase on inflation and on the appreciation of the real exchange rate on one hand, and the Maastricht criteria regarding inflation and exchange rate stability on the other hand. A restrictive monetary policy could succeed in reaching inflation criteria, but only with the cost of slowing down real convergence. This paper deals with the Balassa–Samuelson effect in Romania. The main conclusion of the paper is that in the period 1998–2006 the average annual rate of inflation generated by the Balassa–Samuelson effect in Romania was on average 0.6% in the case of the classical model. Due to the existence of government-regulated prices (mostly non-tradable goods) accounting for as much as 21% of the CPI basket in Romania – the price of non-tradables has increased by less than in the case those prices were market prices. If we include these regulated prices in non-tradable, which is named by us extended model, the impact of Balassa–Samuelson on inflation could have been on average 2.46%. Therefore, the Balassa–Samuelson effect is expected to result into higher inflation with future price liberalization for non-tradables.