Band 66, Heft 3

Natural fluorite is used for growing CaF2 boules from melt by an improved technique. Chemical treatment of the starting ore decomposes the accessory minerals, thus producing small amounts of the oxides of Si, Al, and Fe insoluble in the melt, whereas the overall content of rare earth elements (REEs) of hundreds of μg g−1, remains unchanged. Analytical techniques and optical measurements provide for assessing the concentration range and trends in the distribution of residual metal impurities along the height of the boules. Solid sampling electrothermal atomic absorption spectrometry (SS-ETAAS) gives good reproducibility for impurities’ distribution within a large concentration range of 0.1–10 μg g−1. The concentrations of Zn and Cu determined were found to vary within the lowest tenths of μg g−1 range in the starting portions of chemically treated fluorspar and a batch of boules produced subsequently. The concentrations of both elements show a decreasing trend towards the top section within the confidential interval, the width of which confirms the definite in homogeneities in their distribution at those concentration levels. The Fe occurs in the boules below the detection limit, while the content of lead diminishes rapidly towards their upper section, probably due to a shorter path in the liquid phase before any vapour phase transition proceeds. A satisfactory correlation is found between the Pb concentration in ng g−1-range and light-absorption peak intensity at 204 nm, the precise determination of which is impeded due to the overlapping bands and the light-scattering effect. Reliable determination of impurities enables optimisation of the basic purification — growing stages for the production of high grade crystals.

Tannic acid is commonly employed as the main component in culture media for the selection of tannase-producing strains. In biotechnological processes it is the favorite substrate used to induce the tannase enzyme in both solid and submerged culture for microbial and/or enzymatic production of gallic acid. However, the results found in literature are inconsistent notwithstanding the strict control of all parameters that rule the bioprocesses. The present work, for the first time, reveals the importance of differences in the quality and chemical profile of tannic acid from different suppliers and their influence on the fungal and enzymatic hydrolytic pattern obtained when it is used as a substrate. A degree of hydrolysis between 64.7 % and 100 % has been determined in different tannic acid samples. The specific growth rate of 0.712 h−1, 0.792 h−1, 0.477 h−1, 0.536 h−1 for Jalmek®, Faga Lab®, Division Food®, and Riedel de Häen®, respectively, was obtained at the concentration of 80 g L−1 of each of the tannic acids.

In this work, the performance of three heterogeneous catalysts, namely potassium hydroxide/γ-alumina, bulk calcium oxide, and nano-calcium oxide, in comparison with the homogeneous potassium hydroxide was studied in the transesterification of palm oil to produce methyl esters and glycerol. The physical and chemical properties of the heterogeneous catalysts were thoroughly characterised and determined using a number of analytical methods to assess their catalytic activities prior to transesterification. The reaction products were analysed using liquid chromatography and their properties were quantified based on the American Society of Testing and Materials and United State Pharmacopoeia standard methods. At the 65°C reaction temperature, the oil-to-methanol mole ratio of 1: 15, 2.5 h of the reaction time, and catalyst (φ r = 1: 40), potassium hydroxide, potassium hydroxide/γ-alumina, nano-calcium oxide, and bulk calcium oxide gave methyl ester yields of 97 %, 96 %, 94 %, and 90 %, respectively. The impregnation of γ-alumina with potassium hydroxide displayed a catalytic performance comparable with the performance of potassium hydroxide where the former could be physically separated via filtration resulting in a relatively greater purity of products. Other advantages included the longer reusability of the catalyst and more active sites with lower by-product formation.

Using rare earth nitrates, tryptophan (L), and sodium citrate (NaL′), three new rare earth ternary complexes (Nd-L-L′· 4H2O, Eu-L-L′ · 4H2O, and La-L-L′ · 4H2O) were prepared. The complexes were characterized by IR, molar conductivity, TG-DTA (thermo gravimetric-differential thermal analysis), 1H NMR, and elemental analyses. TG and elemental analyses of the prepared complexes showed good agreement with their stoichiometry. Compared with two individual ligands, IR spectra of synthesized complexes showed dramatic shift and intensity changes; 1H NMR also showed a slight downfield shift. All analytical results of complexes proved constant composition of M-L-L′ · 4H2O (M = rare earth metal, namely Nd, Eu, or La). Animal tests were also performed to study the anti-coagulation time of these complexes considering also the different concentration of complex Nd-L-L′ · 4H2O. PC-12 pheochromocytoma cells were used to study cell adhesion. Compared with ions of rare earth compounds, rare earth ternary complexes have lower cell toxicity, better cell adhesion, and better anticoagulant action.

A new bis(bidentate) azine ligand was prepared by linking (1Z,1′Z)-1,1′-{butane-1,4-diylbis[oxybenzene-4,1-diyl(1Z)ethyl-1-ylidene]}dihydrazine to salicylaldehyde. Two kinds of binuclear copper(II) and nickel(II) complexes with different stoichiometries were prepared. Reaction of bis(azine) ligand with Cu(II) and Ni(II) acetate at a 1: 1 mole ratio gave double-stranded binuclear bis(azine) complexes with stoichiometry [M(L)(H2O)2]2 containing [M(II)N2O2] centres while at a 2: 1 mole ratio, reaction of Cu(II) and Ni(II) chloride with bis(azine) resulted in dinuclear metal complexes with the general stoichiometry [M2(L)Cl2(H2O)2]. Structures of the bis(azine) ligand and its complexes were identified by elemental analysis, IR and UV-VIS spectra, magnetic susceptibility measurements, TGA, and powder XRD. Extraction properties of the bis(azine) ligand towards some transition metal cations and dichromate anions were also reported. It was found that the bis(azine) ligand does not extract cations but it has high extraction ability towards dichromate anions.

TiO2 nanoparticles with different shapes and sizes were synthesised by the sol-gel route in Water/Brij78/Hexane reverse microemulsions. The aqueous cores of these microemulsions were used as nanoreactors to control sol-gel reactions. We studied the effect of water/surfactant mole ratio (W 0) on the morphology, and textural properties of the final products. The materials thus obtained were characterised by different techniques. Thermogravimetric and differential thermal analysis (TG-DTA) was used to study the thermal behaviour of the products and X-ray diffraction (XRD) to identify the crystalline phases. The morphological and textural properties of the products were determined by scattering electron microscopy (SEM) and the Brunauer-Emmett-Teller (BET) method, respectively. We also studied the influence of thermal treatment on the structure and size of the TiO2 particles. The effect of W 0 on the anatase-rutile phase transition temperature was investigated.

The oxidase and dioxygenase reactions of 3,5-di-tert-butylcatechol (DTBC, I) in the presence of V-polyoxometalate were studied. It was found that the addition of a Lewis base quenched the V-polyoxometalate-catalysed catechol dioxygenase reaction and catalysed the oxidase reaction selectively. The existence of V-polyoxometalate accelerates the autoxidation rate of I as demonstrated by the rate measurements. ESR and UV-VIS spectra showed that the Lewis base destroyed the dioxygenation reaction catalyst as formed and restrained its regeneration by suppressing the coordination of catechol radical to vanadium. The by-products of the dioxygenation and oxidation reactions are H2O and H2O2, respectively.

Electrical energy offers numerous benefits for conducting a synthesis, including increased reaction rates, yield enhancements and cleaner chemistries. 5-Aryl-2-(arylamino)-1,3,4-oxadiazoles were synthesised directly from acylthiosemicarbazide on the platinum electrode under controlled potential electrolysis in an undivided cell assembly in acetonitrile.

A novel terbium 2-hydroxymethyl-benzoimidazole-6-carboxylic acid complex has been designed and unique emission changes to fluoride anions in comparison with HSO4−, AcO−, Cl−, Br−, and I− were observed. Then, the complex was encapsulated into an inorganic matrix. The novel hybrid material, with strong green emission was successfully synthesized as an anions receptor in water. More importantly, this hybrid material not only gave luminescence response to F−, but also to HSO4−. Spectroscopic studies demonstrated that the recognition process for fluoride ions can be mainly ascribed to its hydrogen bonding interactions with hydrogen bond donor units (NH and OH). In case of hydrogen sulfate, the sensing effects can be probably attributed to its acidity instead of hydrogen bonding interactions.

Mn inclusion in the oxide based diluted magnetic semiconductor Zn1−x MnxO (x = 0.04, 0.06, 0.08, and 0.10) grown by standard high temperature solid state reaction technique has been studied. The local and average structure of Zn1−x MnxO was characterized by the super resolution technique maximum entropy method and pair distribution function analysis using the X-ray powder data. Magnetic studies on this material using a Vibrating Sample Magnetometer were also carried out to ascertain the doping level in Zn1−x MnxO.

Thermal analysis of the two systems, (NaF/AlF3)-FeF3 and (NaF/AlF3)-FeO, was carried out with three different cryolite ratios. In these systems, “impurity compounds” decreased the temperature of primary crystallisation with decreasing cryolite ratios. From the slope of the dependencies, it can be assumed that the excess of AlF3 plays a more significant role in changes in the “Fe(III)” systems than in “Fe(II)” systems.