Ground-state properties of benzenoid hydrocarbons by simple bond orbital resonance theory approach

π-electron energies and bond orders of benzenoid hydrocarbons with up to five fused hexagons have been considered by the simple Bond Orbital Resonance Theory (BORT) approach. The corresponding ground states were determined according to four BORT models. In the first three models a diagonalisation of the Hückel-type Hamiltonian was performed in the bases of Kekulé, of Kekulé and mono-Claus and of Kekulé and Claus resonance structures, respectively. In the fourth model a simple BORT ansatz was used. According to this ansatz, the ground state is a linear combination of the positive Kekulé structures, all with equal coefficients. It was shown that π-electron energies and bond orders obtained by these models correlate much better with the PPP energies and bond orders than with the Hückel energies and bond orders. This indicates that a simple BORT approach is quite reliable in predicting the more sophisticated PPP results. Concerning the relative performance of the four BORT models, the best results were obtained with the BORT ansatz. The performance deteriorates with the expansion of the basis set. This is attributed to the fact that in these models the improvement of the basis set is not accompanied with the corresponding improvement of the Hamiltonian. Comparing the BORT-ansatz bond orders with the Pauling bond orders, it was shown that BORT-ansatz bond orders correlate much better with the PPP bond orders. 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.     

In Situ Amperometric Detection of Vesicles and Microgel Phases in an Aggregating System: Calcium Alginate

In situ amperometric characterization of an aggregating system in terms of molecular adsorption and single microparticle interactions at the electrode interface is demonstrated using a model system: alginate/Ca(II) in an aqueous electrolyte solution. Recording of chronoamperometric curves of oxygen reduction at the dropping mercury electrode is designed for detection of dip‐shaped signals of individual gel microparticles. By addition of Ca(II) decrease of alginate adsorption is accompanied by appearance of signals indicating vesicle type association of alginate molecules and microparticles of gel phase. AFM imaging provided evidence of initial stage in calcium alginate gel formation.     

A simple method for the calculation of π-bond orders in alternant hydrocarbons

A new method for the calculation of bond orders in alternant hydrocarbons is presented. The method requires a summation over the contributions of various superposition diagrams. Quantitatively, the method is almost as reliable as PPP, and due to its simplicity it can be used for fast and relatively accurate calculation of bond orders. In addition some simple rules are derived, which in many cases can be used to predict the signs of bond orders between nonbonded atoms.Dedicated to Professor J. Koutecký on the occasion of his 65th birthdayResearch supported by the Robert A. Welch Foundation of Houston, Texas     

UV-densitometric method for the determination of estrogens and androgens in pharmaceutical preparations

Summary UV Densitometric Method for the Determination of Estrogens and Androgens in Pharmaceutical Preparations A convenient method for the determination of estradiol benzoate/testosterone propionate and of ethynylestradiol/methyltestosterone mixtures from ampoules and lingualets, is described. The procedure is simple since the method involves direct reading from the thin-layer plate, avoiding thus the elution of the spot.After TL Chromatographie separation of active substances, densitometric measurements were performed with a HPTL scanner at 254 nm, whereby good and precise results were obtained. The standard deviation was found to range from 0.022 to 0.183, whereas the relative standard deviation ranged from 0.93 to 2.7%.The results obtained show that the method is applicable to routine analysis.     

Preparation and practical application of spinel pigment Co0.46Zn0.55(Ti0.064Cr0.91)2O4

Synthesis of the green spinel pigment Co_0.46Zn_0.55(Ti_0.064Cr_0.91)₂O₄ by a novel two-step method of preparation have been investigated. Inorganic pigments are almost always prepared by a solid state reaction. It is classical ceramic method which used oxides, hydroxides or carbonates as precursors. The reaction is performed at temperature higher than 1300°C and an agent of mineralization is usually present. The presented novel method of preparation decreases the calcining temperature necessary for reaching of bright and clear hue of the pigments prepared. Main attention was focused on the influence of two types of titanium raw materials on the temperature region of the spinel structure formation and on the colour properties of the pigments. The mixture of precursors with TiO₂ gives a one-phase system when calcining at 1100°C but the colour properties are more interesting at 1150°C. Thermal stability of this pigment is limited by temperature 1300°C. This temperature is connected with partial oxidation of Cr(III) to Cr(VI). Thermal analysis provided the first information about the temperature region of the pigment formation and determined the thermal stability of pigment.     

Poly(ethylene glycol) as Impregnator for Silica Gel in Salting-Out Thin-Layer Chromatography of Some Co(III) Complexes

Silica gel impregnated with poly(ethylene glycol) of different molecular mass (400, 1000, 1540, 4000, and 5500) was investigated for salting-out thin-layer chromatography of 15 mixed aminocarboxylato Co(III) complexes using eight ammonium sulphate solutions as mobile phases. Regularities established earlier for non-impregnated adsorbents are also valid in this work. Poly(ethylene glycol) of high molecular mass increases the hydrophobicity of the adsorbent. Positive linear dependence of R_M values and of salting-out efficiency on average poly(ethylene glycol) molecular mass was usually observed. In contrast with non-impregnated silica gel, separation was achieved between complexes with the smallest hydrocarbon groups.     

Thin-Layer Chromatographic Analysis of Flavonoids,Phenolic Acids,and Amino Acids in Some Croatian Hypericum Taxa

JPC – Journal of Planar Chromatography – Modern TLC - The flowering tops of Hypericum hirsutum, H. montanum, H. perforatum subsp. angustifolium, H. perforatum subsp. perforatum, and H....     

HF heating of a plasma column at frequencies below the electron cyclotron frequency

Dispersion of waves, excited by the helical structure in a plasma column and the heating of a tail of the electron distribution function is studied at frequencies below the electron plasma and the electron cyclotron frequency.We wish to thank Dr. R.Klíma for valuable discussions and Dr. J.Lacina and Mrs. P.Jaroová for the computational work. We also thank Dr. L.Bárdo, Dr. L.Kryka and Dr. G. L.Khorosanov from Sukhumi Institute, USSR, for their help during different stages of the experiment. We are indebted to Mr. J.Dvoák, Mr. F.Jiránek and Mr. B.usta for their expert technical assistance.