Use of x-ray fluorescence spectrometry in ion-exchange studies of leach liquors

Equilibrium and kinetic studies of ion exchange of a complex leach liquor from coal ash, with strongly basic resins and a liquid ion exchanger are reported. The multi-component system was studied by determining the composition of the effluents and by non-destructive analysis of the loaded ion exchangers by XRF spectrometry. In the case of column operation, the elution processes were investigated by the same method, which was very appropriate for non-destructive monitoring of resin regeneration steps done repeatedly with the same resin sample.     

On lower bounds of number of perfect matchings in fullerene graphs

Couting perfect matchings in graphs is a very difficult problem. Some recently developed decomposition techniques allowed us to estimate the lower bound of the number of perfect matchings in certain classes of graphs. By applying these techniques, it will be shown that every fullerene graph with p vertices contains at least p/2+1 perfect matchings. It is a significant improvement over a previously published estimate, which claimed at least three perfect matchings in every fullerene graph. As an interesting chemical consequence, it is noted that every bisubstituted derivative of a fullerene still permits a Kekulé structure.     

Thermal decomposition of N2H6GeF6 · H2O,isolation and characterization of intermediates

The thermal behaviour of N₂H₆GeF₆ · H₂O was investigated by TG, DTG and DTA measurements. The decomposition proceeded in three steps, in which anhydrous N₂H₆GeF₆ and N₂H₅GeF₅; were isolated and characterized by chemical analysis and vibrational spectroscopy. The X-ray powder photographs of the intermediates were indexed, namely, for N₂H₆GeF₆ on the basis of a monoclinic cell with a = 8.86(9), b = 9.29(2), c =7.40(0) Å, β = 85° and for N₂H₅GeF₅ on the basis of an ortrhorhombic cell with a = 8.43(5),b = 9.19(9), c = 7.43(6) Å.     

Delphinidin–Aluminum(III) Complexes in Aqueous and Non-Aqueous Media: Spectroscopic Characterization and Theoretical Study

Summary. The study of delphinidin complexation with trivalent aluminum in acidic aqueous buffered (pH 3.0 and 3.8) and methanolic solutions was performed utilizing electronic absorption spectroscopy and quantum chemical calculations. In its structure delphinidin possesses several chelating sites in competition towards aluminum(III). Molar ratio plots denoted the formation of only one aluminum(III):delphinidin complex of stoichiometry of 1:1 in both investigated media. Semiempirical calculations, performed at the restricted HF AM1 level, enabled the determination of the structural features of free delphinidin and structural modifications caused by chelation of aluminum(III). Considering the pigment molecular structure and the results of the theoretical calculations it is possible to equally implicate C3′–C4′ and C4′–C5′ hydroxyl groups as those with the predominant chelating power.     

Reactions of substituted furo[3,2-<Emphasis Type="Italic">b</Emphasis>]pyrrole-5-carboxhydrazides and their biological activity

The reactions of substituted furo[3,2-b]pyrrole-5-carboxhydrazides 1 with 5-arylfuran-2-carboxaldehydes 2, 4,5-disubstituted furan-2-carboxaldehydes 3 and thiophene-2-carboxaldehyde 4 has been studied. The advantage of microwave irradiation on some of these reactions was reflected in the reduced reaction time and increased yields. Reactions of 1 with 4-substituted 1,3-oxazol-5(4H)-ones 11 led to diacylhydrazines 13 or to imidazole derivatives 14 depending on the temperature. 1,2,4-Triazole-3-thione 17 was synthesized by two-step reaction of 1 with phenylisothiocyanate and subsequent base-catalyzed cyclization of thiosemicarbazide 16. The effects of hydrazones 5–10 on inhibition of photosynthetic electron transport in spinach chloroplasts and chlorophyll content in the antialgal suspensions of Chlorella vulgaris were investigated.     

Crystal structures and magnetic properties of two low-dimensional materials constructed from [Mn(III)(salen)H2O]+ and [M(CN)8](3-/4-) (M = Mo or W) precursors

The syntheses, X-ray structures, and magnetic behaviors of two new cyano-bridged assemblies, the molecular [Mn(III)(salen)H2O]3[W(V)(CN)8].H2O (1) and one-dimensional [Mn(salen)(H2O)2]2[[Mn(salen)(H2O)][Mn(salen)]2[Mo(CN)(8)]].0.5ClO4.0.5OH.4.5H2O (2), are presented. Compound 1 crystallizes in the monoclinic system, has space group P2(1)/c, and has unit cell constants a = 13.7210(2) A, b = 20.6840(4) A, c = 20.6370(2) A, and Z = 4. Compound 2 crystallizes in the triclinic system, has space group P, and has unit cell dimensions a = 18.428(4) A, b = 18.521(3) A, c = 18.567(4) A, and Z = 2. The structure of 1 consists of the asymmetric V-shaped Mn-NC-W-NC-Mn-O(phenolate)-Mn molecules, where W(V) coordinates with [Mn(salen)H2O] and singly phenolate-bridged [Mn(salen)H2O]2 moieties through the neighboring cyano bridges. The [W(V)(CN)8]3- ion displays distorted square-antiprism geometry. The structure of 2 consists of the cyano-bridged [Mn3(III)Mo(IV)]n- repeating units linked by double phenolate bridges into one-dimensional zigzag chains. The Mn(III) centers are bound to Mo(IV) of square-antiprism geometry through the neighboring cyano bridges. The magnetic studies of 1 reveal the antiferromagnetic intramolecular interactions through the CN and phenolate bridges and the relatively weak intermolecular interactions. Compound 1 becomes antiferromagnetically ordered below TN = 4.6 K. The presence of the magnetic anisotropy is documented with the MH measurements carried out for both polycrystalline and single-crystal samples. At T = 1.9 K, the spin-flop transition is observed in the field of 18 kOe applied parallel to the bc plane, which is the easy plane of magnetization. Field dependence of magnetization of 1 shows field-induced metamagnetic behavior from the antiferromagnetic ground state of ST = 3/2 to the state of ST = 5/2. The magnetic properties of 2 indicate a weak antiferromagnetic interaction between Mn(III) centers in double-phenolate-bridged [Mn(III)(salen)]2 dinuclear subunits and a very weak ferromagnetic interaction between them through the diamagnetic [Mo(IV)(CN)8]4- spacer.     

Fluoroapatite - material for medicine,Growth, morphology and thermoanalytical properties

Fluoroapatite containing glass-ceramics were prepared from Li₂O-CaO-CaF₂-P₂O₅-SiO₂ system. The glass was melted at 1480°C for 1 h. The object of observation was the preparing crystal phase of fluoroapatite in amorphous glass matrix. The morphology of lithium disilicate glass-ceramics was studied by SEM. The crystal growth and thermal properties of fluoroapatite were studied by X-ray diffraction and DTA. The more the content of P₂O₅, the more the presence of fluoroapatite particles. SEM investigation clearly indicated the phase separation and formation of a primary crystalline phase of fluoroapatite in the studied glass-ceramics. DTA curves of the fluoroapatite samples exhibit exothermic effects in the temperature range 337-694°C depending on the composition of the materials. The position of exothermic peak for lithium disilicate on DTA curves moves with increasing specific surfacetowards lower temperatures which points on its preferential surface crystallization. As far as physical qualities are concerned, mainly color and gloss, the best qualities of all observed materials belong to glass-ceramics with 10% P₂O₅. This revised version was published online in July 2006 with corrections to the Cover Date.     

Heterogeneous reactions of solid nickel(II) complexes,V

The kinetics of the thermal decomposition of solid complexes of the type Ni(NCS)₂L₂ (L=pyridine,β-picoline and quinoline), of pseudooctahedral configuration, were studied by using isothermal methods, on the basis of losses of weight, in the temperature range 90–191?. The most suitable reaction order for all the complexes under investigation was found to ben=2/3, i.e. the total decomposition rate is determined by the chemical process proper. The calculated values ofE _a(in kcal · mole^?1) decrease in the following order: Ni(NCS)₂py₂ (29.4)>Ni(NCS)₂(β-pic)₂ (27.6)>Ni(NCS)₂Q₂ (24.3). With increasing volume of the ligand L the reaction rate also increases, and this suggests that the reaction proceeds by dissociative activation. For all the investigated complexes it was found that δH>E _A; this may be explained by a several-step mechanism and the complex Ni(NCS)₂L is then considered an intermediate.     

Synthesis and properties of water-soluble gold colloids covalently derivatized with neutral polymer monolayers

Citrate-capped gold nanoparticles as well as planar gold surfaces can be efficiently grafted with a covalently attached polymer monolayer a few nanometers thick, by simple contact of the metal surface with dilute aqueous solutions of hydrophilic polymers that are end-capped with disulfide moieties, as shown by UV/vis absorption, dynamic light scattering, and surface plasmon resonance studies. The hydrophilic polymer-coated gold colloids can be freeze-dried and stored as powders that can be subsequently dissolved to yield stable aqueous dispersions, even at very large concentrations. They allow for applying filtrations, gel permeation chromatography, or centrifugation. They do not suffer from undesirable nonspecific adsorption of proteins while allowing the diffusion of small species within the hydrogel surface coating. In addition, specific properties of the original hydrophilic polymers are retained such as a lower critical solution temperature. The latter feature could be useful to enhance optical responses of functionalized gold surfaces toward interaction with various substrates.