A pyrimidine thiolate Rh(I) complex: structure, bonding and one-dimensional interactions in solid and in solution

The reaction of [Rh(micro-Cl)(COD)]2 with 4,6-dimethyl-pyrimidinethiolate (Me2-pymt) and subsequent substitution of COD by CO yields [Rh(Me2-pymt)(CO)2]. The stacking pattern found in this compound is in contradiction with previously studied comparable square-planar complexes of type d8-[M(chelate)(monodentate)2] in which each ligand has different pi-acidic character. A theoretical study of the intermolecular interactions and conformation of the title compound has been carried out, combining semi-empirical band calculations on the real chains and ab initio(MP2 level) calculations on a model dimer. The combination of electronic and steric effects determines the rotation of the successive monomers and the deviation from linearity of the one-dimensional stacks. Its behaviour in solution is also special, developing a blue colour and forming micelles, when adding water to acetone solutions.     

Highly enantioselective Cu-catalysed asymmetric 1,4-addition of diphenylzinc to cyclohexenone

Highly enantioselective Cu-catalysed 1,4-addition of diphenylzinc to cyclohexenone has been achieved for the first time using a monodentate phosphoramidite ligand.     

Determination of molybdenum, chromium and aluminium in human urine by electrothermal atomic absorption spectrometry using fast-programme methodology

Rapid and direct procedures for the determination of molybdenum, chromium and aluminium in human urine samples are developed. Fast-programme methodology is used to simplify the heating cycles. Hydrogen peroxide, nitric acid and Triton X-100 are added to the urine samples which are directly introduced into the furnace. For molybdenum, two successive injection steps are required due to the low level of this element in the samples analyzed. Calibration is carried out using aqueous standards for aluminium and the standard additions method for both molybdenum and chromium. The reliability of the procedures is checked by analyzing two certified reference materials.     

Studies of the soluble part of oxidised coals

Soluble products obtained from the oxidation of four types of coal, each characterised by different degree of coalification and different degree of sulphur content, are studied. The coals are oxidised with peracetic acid (PAA) and nitric acid. Analyses are performed by Atmospheric Pressure-Temperature Programmed Reduction (AP-TPR) and Fourier Transform Infrared Spectroscopy (FTIR). The soluble products contain much more sulphur than the insoluble products of oxidation. The products obtained from the reaction with HNO₃ contain higher amounts of inorganic sulphur compounds, while those obtained from the reaction with PAA are characterised by an increased content of organic sulphur species.     

Performance of an internal-loop airlift bioreactor for treatment of hexane-contaminated air

Hexane is a toxic volatile organic compound that is quite abundant in gas emissions from chemical industries and printing press and painting centers, and it is necessary to treat these airstreams before they discharge into the atmosphere. This article presents a treatment for hexane-contaminated air in steady-state conditions using an internal-loop airlift bioreactor inoculated with a Pseudomonas aeruginosa strain. Bioprocesses were conducted at 20-mL/min, a load of 1.26 g/m³ of C₆H₁₄, and a temperature of 28°C. The results of hexane removal efficiencies were presented as a function of the inoculum size (approx 0.07 and 0.2 g/L) and cell reuse. Bioprocess monitoring comprises quantification of the biomass, the surface tension of the medium, and the hexane concentration in the fermentation medium as well as in the inlet and outlet airstreams. The steady-state results suggest that the variation in inoculum size from 0.07 to 0.2 g/L promotes hexane abatement from the influent from 65 to 85%, respectively. Total hydrocarbon removal from the waste gas was achieved during experiments conducted using reused cells at an initial microbial concentration of 0.2 g/L.     

Desorption of chloroorganic compounds from a bed of activated carbon

The desorption of 1,2-dichloroethane from a bed of DTO activated carbon after adsorption from aqueous solution has been investigated. The desorption process was carried out using steam. The basic characteristics of the process were determined. The studies were performed in the temperature range 100-160 degrees C. A steam consumption indicator reduces with an increase of temperature from 100 to 140 degrees C. An elevation of temperature above 140 degrees C does not cause an improvement in the desorption efficiency. The number of performed cycles does not reduce the adsorption capacity of used activated carbon. Studies on the regeneration of the bed saturated with a seven-component mixture of chloroorganic compounds at temperature of 140 degrees C were carried out. The degree of removal of the sum of chloro-derivatives exceeded 0.96 at a volume ratio of steam (recalculated on the condensate) to bed of about 10. It was found that the dechlorination proceeds during desorption at elevated temperature. The quantitative ratio of chloro-derivatives in the desorbate was changed in comparison to the composition of wastewater directed to the adsorption.     

Creatinine biosensor based on ammonium ion selective electrode and its application in flow-injection analysis

A new, highly sensitive, fast responding and stable potentiometric biosensor for creatinine determination is developed. The biosensor is based on an ammonium ion-selective electrode. Creatinine deiminase (EC 3.5.4.21) is chemically immobilized on the surface of the polymeric ion-sensitive membrane in the form of monomolecular layer using a simple, one-step carbodiimide covalent attachment method. The resulting enzyme electrodes are useful for measurement under flow injection analysis (FIA) conditions. The biosensors exhibit excellent operational and storage stability. The enzyme electrodes retain over 70% of initial sensitivity after ten weeks of work under FIA conditions. The storage stability at 4 °C is longer than half a year without loss of sensitivity. Under optimized conditions near 30 samples per hour can be analyzed and the determination range (0.02-20.0 mmol l⁻¹) fully covers creatinine concentrations important from clinical and biomedical point of view. The simple biosensor/FIA system has been successfully used for determination of creatinine in urine, serum and posthemodialysate samples.     

SANS study of the aging of xTiO2-SiO2 gels

Silica-titania gels, prepared in acidic conditions, with contents of TiO₂ up to 6 mol%, have been studied by small angle neutron scattering (SANS) as wet gel with increasing aging times. In all samples, small primary particles have been found with a diameter of about 3 nm. At the gel point, cylindrical clusters, ca. 10 nm long, were observed as well. These grow with aging time, becoming branched. The cluster-cluster diffusion limited aggregation model is found to be consistent with the SANS results. The growth process is independent of the TiO₂ content. It is mainly influenced by the ratio of the aging time to the gelation time.     

A Novel Reductive Cyclization of o-Nitrobenzamides and Ketones Promoted by Low-valent Titanium Reagent

A short and facile synthesis of a series of 1,2-dihydroquiazolin-4(3H)-ones was accomplished in good yields via novel reductive cyclization of o-nitrobenzamides with ketones promoted by TiCI4/Zn system. The structure was established on the basis of elemental analysis, IR,^1H NMR and confirmed by a single-crystal X-ray diffraction analysis. This method has the advantages of easily accessible starting materials, convenient manipulation and moderate to high yields.     

异丙氧基-异羟肟酸-氧钒（V）配合物的合成、晶体结构和量子化学研究

以苯甲酰异羟肟酸为配体，首先合成四价氧钒化合物，以此为基础合成了标题 化合物，并用元素分析，红外光谱，~1H NMR，~(13)C NMR，~(15)V NMR，电子吸 收光谱等，分别对它进行了表征，其结构用单晶X射线衍射法测定，晶体属三斜晶 系，P1-bar空间群，所得晶体学参数为a = 1.1119(3) nm，b = 1.1735(3) nm，c = 0.8660(2) nm，α = 96.84(1)°，β = 106.93)(1)°，γ = 88.97(1)°，V = 1.0731(2) nm~3，D_c = 1.415 g/cm~3，Z = 2，F(000) = 478，μ = 5.06 cm~(-1)。采取ab initio(GTO-6-31d)方法对标题化合物的结构单元的成键情况进 行了分析，讨论了化合物的稳定性、分子轨道能量、原子静电荷分布等情况。