69mZn-containing radiopharmaceuticals: a novel approach to molecular design

^69mZn was produced and separated for medical applications. Possibilities and perspectives for production of radiopharmaceuticals based on ^69mZn containing derivatives of thiazine, thiazoline and thiourea are considered. Each one of the latters is a zinc chelator and a nitric oxide synthase (NOS) effector at the same time. Cytotoxic effect of NOS activator and NOS inhibitors are shown in experiments with HL-60, K-562 and MOLT-4 cell lines and in bone marrow cells of the acute B-lymphoblastic leukemia patients. Some of those compounds are worthy to get selected for further application as radiopharmaceuticals including their antitumor speciements.

     

Analysis of cardiovascular oscillations: a new approach to the early prediction of pre-eclampsia

Pre-eclampsia (PE) is a serious disorder with high morbidity and mortality occurring during pregnancy; 3%-5% of all pregnant women are affected. Early prediction is still insufficient in clinical practice. Although most pre-eclamptic patients show pathological uterine perfusion in the second trimester, this parameter has a positive predictive accuracy of only 30%, which makes it unsuitable for early, reliable prediction. The study is based on the hypothesis that alterations in cardiovascular regulatory behavior can be used to predict PE. Ninety-six pregnant women in whom Doppler investigation detected perfusion disorders of the uterine arteries were included in the study. Twenty-four of these pregnant women developed PE after the 30th week of gestation. During pregnancy, additional several noninvasive continuous blood pressure recordings were made over 30 min under resting conditions by means of a finger cuff. The time series extracted of systolic as well as diastolic beat-to-beat pressures and the heart rate were studied by variability and coupling analysis to find predictive factors preceding genesis of the disease. In the period between the 18th and 26th weeks of pregnancy, three special variability and baroreflex parameters were able to predict PE several weeks before clinical manifestation. Discriminant function analysis of these parameters was able to predict PE with a sensitivity and specificity of 87.5% and a positive predictive value of 70%. The combined clinical assessment of uterine perfusion and cardiovascular variability demonstrates the best current prediction several weeks before clinical manifestation of PE.     

Structure–property relations for balsa wood as a function of density: modelling approach

In order to find an alternative core material to balsa wood in composite sandwich structures, it is important to understand balsa’s elastic properties in relation to its complex microstructural organisation. In the present work, experimental data on the elastic constants and microstructural features of balsa wood were collected for different porosities (densities) and processed into structure–property relations. An inverse problem was solved to predict variation of the cell wall properties with density, such that the collected experimental structure–property relations were satisfied. The Young’s modulus of the cell wall material in the longitudinal direction was found to increase with balsa’s density, which is consistent with the knowledge that the cell wall material stiffens during tree maturation. The value reported in the literature falls in the middle of the predicted range. The proposed micromechanical model also accurately calculated elastic properties of balsa wood at the mesolevel including longitudinal, radial, and tangential directions. The model took into account the presence of ray cells. It was shown that the addition of 15 % of rays increased the radial Young’s modulus up to 4 times with only slight decrease in the longitudinal modulus.     

On the two-step method for solving nonlinear equations with nondifferentiable operator

We study a local and a semilocal convergence of the two-step method for solving nonlinear equations with a nondifferentiable operator. Its method is based on two methods of order of convergence . We carry out the numerical research on test problems and do the comparison of obtained results. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

On an one-step modification of Gauss-Newton method under generalized Lipschitz conditions for solving the nonlinear least squares problem

We investigate convergence of the one-step modification of Gauss-Newton method using the divided differences and the weak generalized Lipschitz condition for the divided differences. Convergence order of the method was examined and the uniqueness ball for the solution of the nonlinear least squares problem was proved. Numerical experiments were also provided. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Direct palladium-catalyzed arylation of cyclopropenes

The first examples of direct palladium-catalyzed arylation and heteroarylation of cyclopropenes have been demonstrated. This method allows for efficient synthesis of various tetrasubstituted cyclopropenes, incuding nonracemic cyclopropenes, which are not available via known asymmetric cyclopropenation methods. Mechanistic studies strongly suggest an electrophilic path for this Heck-type transformation.     

Gas chromatography-mass spectrometry analysis of alkylphenols in produced water from offshore oil installations as pentafluorobenzoate derivatives

A simple, highly selective and sensitive method for the determination of 14 representative alkylphenols from phenol (C0) to nonylphenol (C9) in produced water is described. Solid-phase extraction (SPE) by anion-exchange sorbent is used to extract alkylphenols from produced water. The samples are then derivatised by pentafluorobenzoyl chloride and analysed on GC-MS (negative ion chemical ionisation, NCI). The derivatisation procedure has been validated by means of two-level factorial design (2(7-4)) experiments. Quantification is done with isotope dilution of five internal standards of different alkyl chain length. The detection limits were at low ng/l levels. A comparison with GC-MS analysis of non-derivatised alkylphenol samples revealed the advantage of derivatisation as described in the method.     

Photopolymerization of water-soluble acrylic monomers induced by colloidal CdS and Cd x Zn1 − x S nanoparticles

Photocatalytic activity of CdS and Cd _x Zn_1−x S nanoparticles in the polymerization of acrylamide and acrylic acid in aqueous solutions has been found. It has been shown that the most probable way of the photogeneration of primary radicals is the reduction of an adsorbed monomer by the conduction band electrons of the semiconductor nanoparticles, a monomer oxidation by the valence band holes and atomic hydrogen addition to a monomer being complementary photoinitiation routes. A correlation between the composition of Cd_xZn_1-xS nanoparticles and their photocatalytic activity in the acrylamide polymerization has been established. It has been shown that an increase in the quantum yield of the photopolymerization in a sequence СdS < Cd_0.75Zn_0.25S < CdS_0.5Zn_0.5S < Cd_0.3Zn_0.7S originates from a concurrent increase of the conduction band potential of the semiconductor nanoparticles. A kinetic equation of the photocatalytic acrylamide polymerization has been derived. Quantum yields of the photoinitiation have been found to be as small as 10⁻⁴ to 10⁻³.     

Photocatalytic hydrogen evolution over mesoporous TiO2/metal nanocomposites

Na⁺ complex with the dibenzo-18-crown-6 ester was used as a template to synthesize mesoporous titanium dioxide with the specific surface area 130–140 m²/g, pore diameter 5–9 nm and anatase content 70–90%. The mesoporous TiO₂ samples prepared were found to have photocatalytic activity in Cu^II, Ni^II and Ag^I reduction by aliphatic alcohols. The resulting metal–semiconductor nanostructures have remarkable photocatalytic activity in hydrogen evolution from water–alcohol mixtures, their efficiency being 50–60% greater than that of the metal-containing nano-composites based on TiO₂ Degussa P25.The effects of the thermal treatment of mesoporous TiO₂ upon its photocatalytic activity in hydrogen production were studied. The anatase content and pore size were found to be the basic parameters determining the photoreaction rate. The growth of the quantum yield of hydrogen evolution from TiO₂/Ag⁰ to TiO₂/Ni⁰ to TiO₂/Cu⁰ was interpreted in terms of differences in the electronic interaction between metal nanoparticles and the semiconductor surface. It was found that there is an optimal metal concentration range where the quantum yield of hydrogen production is maximal. A decrease in the photoreaction rate at further increment in the metal content was supposed to be connected with the enlargement of metal nanoparticles and deterioration of the intimate electron interaction between the components of the metal–semiconductor nanocomposites.     

A Novel Metastable Pentavalent Plutonium Solid Phase on the Pathway from Aqueous Plutonium(VI) to PuO2 Nanoparticles

Here we provide evidence that the formation of PuO₂ nanoparticles from oxidized Pu^VI under alkaline conditions proceeds through the formation of an intermediate Pu^V solid phase, similar to NH₄PuO₂CO₃, which is stable over a period of several months. For the first time, state‐of‐the‐art experiments at Pu M₄ and at L₃ absorption edges combined with theoretical calculations unambiguously allow to determine the oxidation state and the local structure of this intermediate phase.