The effect of adding a standard on the result of determination of polychlorinated biphenyls in bottom sediment samples

Bottom sediments are a very important component of aquatic ecosystems. The sediment matrix is highly diverse and heterogeneous; in consequence, compounds entering the aquatic environment from different sources are considerably enriched at its surface. Bottom sediments are regarded as natural sorbents, since they accumulate many harmful substances, such as heavy metals and stable organic contaminants.Extraction is a key stage in every analytical procedure. It is during this stage that standards are added to samples. Standards are necessary not only for estimating analyte yields but also for validating the whole procedure. The question of the addition of standard substances to sediment samples has not been widely addressed in the subject literature, and yet it is of fundamental importance as regards obtaining reliable results of determinations.This paper describes the results of a study on the effect of standard addition techniques on the results of determination of polychlorinated biphenyls in sediment samples (certified reference material: METRANAL™2—river sediment).     

Influence of photodynamic effect on biological activity of PBR–PP complexes

The aim of this study was to examine the influence of photodynamic effect on biological activity of PBR–PP complexes. These measurements were performed in pH dependent environment. Constant concentration of solubilized receptor was titrated with increasing concentration of porphyrins (PPIX, Hp, PP(Arg)₂, Hp(Arg)₂, PP(Gly)₂, PP(Ala)₂, PP(Ser)₂, PP(Phe)₂) and binding constants were calculated. PBP–PP mixtures were illuminated with 3 J, 5 J or 10 J of blue light and changes in protein fluorescence was recorded. Experimental data were fitted to weak and strong binding models. As a result for all derivatives weak binding model was the best fitted. The strongest binding showed PPIX in pH 7.4 and with pH drop binding constants showed greater values for all examined derivatives. Out of amino acid derivatives the strongest binding was noticed for PP(Gly)₂ and PP(Phe)₂ and for the last one pH influence was not observed.     

Determination of PAHs, PCBs, minerals, trace elements, and fatty acids in Rapana thomasiana as an indication of pollution

The aim of this investigation was to introduce several analytical methods for determination of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), minerals, trace elements, and fatty acids in Rapana thomasiana as a marine pollution indicator organism. The chemical differences of the gastropod Ra. thomasiana from polluted and nonpolluted sites of the Black Sea on the Bulgarian coast were investigated. Chromatography and high-resolution inductively coupled plasma/MS analyses were used for evaluation of PAHs, PCBs, fatty acids, minerals, and trace elements. These methods can be applied to other marine products.     

Investigation effect of benzotriazole on the corrosion of brass-MM55 alloy in artificial seawater by dynamic EIS

The electrochemical behavior of brass-MM55 alloy was studied in artificial seawater with benzotriazole by using a novel method called dynamic electrochemical impedance spectroscopy (DEIS). This method gives possibility to investigate the protection of metals in corrosive medium by using inhibitors in galvanostatic conditions for a long time. Instantaneous impedance spectra for brass-MM55 were recorded for 10 h in artificial seawater for different concentration of benzotriazole. It was found that a few hours were not enough for the accurate calculation of corrosion inhibition. Also with this method it is possible to figure out how the charge transfer resistance (R _ct) changes by the time. Usefulness of the DEIS technique in the investigation of non-stationary phenomena has been proved in the field of inhibitor research. All studies clearly show that benzotriazole inhibits the corrosion of brass-MM55 alloy in artificial seawater solution and the value of inhibition efficiency increases with increasing concentration of benzotriazole.     

Application of the elongation method to the electronic structure of spin-polarized molecular wire under electric field

The elongation method has been applied to elucidate the spin-dependent behavior of the pyrrole-based spin-polarized molecular wire containing 1-pyrrolylphenyl nitronyl nitroxide with oligothiophene units under the influence of an applied electric field. It was found that the donor pyrrole ring causes the delocalization of electrons over the molecular wire regardless of the spin-orientation. In addition, nitronyl nitroxide as a radical unit shows two important features. First, it changes the spin-distribution of the delocalized electrons from same ratio of α- and β-spins to dominant β-spin. Second, it shifts the distribution of electrons in the same direction as that of the applied electric field.     

Quantitative SNIFTIRS studies of (bi)sulfate adsorption at the Pt(111) electrode surface

Subtractively normalized interfacial Fourier transform infrared reflection spectroscopy (SNIFTIRS) was applied to study (bi)sulfate adsorption on a Pt(111) surface in solutions of variable pH while maintaining a constant total bisulfate/sulfate ((bi)sulfate) concentration without the addition of an inert supporting electrolyte. The spectra were recorded for both the p- and s-polarizations of the IR radiation in order to differentiate between the IR bands of the (bi)sulfate species adsorbed on the electrode surface from those species located in the thin layer of electrolyte. The spectra recorded with p-polarized light consist of the IR bands from both the species adsorbed at the electrode surface and those present in the thin layer of electrolyte between the electrode surface and ZnSe window whereas the s-polarized spectra contain only the IR bands from the species located in the thin layer of electrolyte. A new procedure was developed to calculate the angle of incidence and thickness of the electrolyte between the Pt(111) electrode surface and the ZnSe IR transparent window. By combining these values with the knowledge of the optical constants for Pt, H(2)O and ZnSe, the mean square electric field strength (MSEFS) at the Pt(111) electrode surface and for thin layer of solution were accurately calculated. The spectra recorded using s-polarization were multiplied by the ratio of the average MSEFS for p- and s-polarizations and subtracted from the spectra recorded using p-polarization in order to remove the IR bands that arise from the species present within the thin layer cavity. In this manner, the resulting IR spectra contain only the IR bands for the anions adsorbed on the Pt(111) electrode surface. The spectra of adsorbed anions show little change with respect to the pH ranging from 1 to 5.6. This behavior indicates that the same species is predominantly adsorbed on the metal surface for this broad range of pH values and the results suggest that sulfate is the most likely candidate for this adsorbate.     

How do sterols determine the antifungal activity of amphotericin B? Free energy of binding between the drug and its membrane targets

Amphotericin B (AmB) is a well-known polyene antibiotic used to treat systemic fungal infections. It is commonly accepted that the presence of sterols in the membrane is essential for the AmB biological activity, that is, for the formation of transmembrane ion channels. The selective toxicity of AmB for fungal cells is attributed to the fact that it is more potent against fungal cell membranes containing ergosterol than against the mammalian membranes with cholesterol. According to the "primary complex" hypothesis, AmB associates with sterols in a membrane to form binary complexes, which may subsequently assemble into a barrel-stave channel. To elucidate the molecular nature of the AmB selectivity for ergosterol-containing membranes, in the present work, we used computational methods to study the formation of the putative AmB/sterol complexes in a lipid bilayer. The free energy profiles for the AmB-sterol association in phospholipid bilayers containing 30 mol % of sterols were calculated and thoroughly analyzed. The results obtained confirm the formation of specific AmB/ergosterol complexes and are used to determine the energetic and structural origin of the enhanced affinity of AmB for ergosterol than for cholesterol. The significance of this affinity difference for the mechanism of action of AmB is discussed. The data obtained allowed us also to suggest a possible origin of the increased selectivity of a novel class of less toxic AmB derivatives.     

Screening of transformation products in soils contaminated with unsymmetrical dimethylhydrazine using headspace SPME and GC-MS

The paper describes a novel SPME-based approach for sampling and analysis of transformation products of highly reactive and toxic unsymmetrical dimethylhydrazine (UDMH) which is used as a fuel in many Russian, European, Indian, and Chinese heavy cargo carrier rockets. The effects of several parameters were studied to optimize analyte recovery. It was found that the 85 μm Carboxen/polydimethylsiloxane fiber coating provides the highest selectivity for selected UDMH transformation products. Optimal sampling/sample preparation parameters were determined to be 1-h soil headspace sampling time at 40 °C. The GC inlet temperature was optimized to 170 °C held for 0.1 min, then 1 °C s⁻¹ ramp to 250 °C where it was held for 40 min. Temperature programing resulted in a fast desorption along with minimal chemical transformation in the GC inlet. SPME was very effective extracting UDMH transformation products from soil samples contaminated with rocket fuel. The use of SPME resulted in high sensitivity, speed, small labor consumption due to an automation and simplicity of use. It was shown that water addition to soil leads to a significant decrease of recovery of almost all target transformation products of UDMH. The use of SPME for sampling and sample preparation resulted in detection of the total of 21 new compounds that are relevant to the UDMH transformation in soils. In addition, the number of confirmed transformation products of UDMH increased from 15 to 27. This sampling/sample preparation approach can be recommended for environmental assessment of soil samples from areas affected by space rocket activity.     

Dimension and measure for semi-hyperbolic rational maps of degree 2

We prove that almost every non-hyperbolic rational map of degree 2 has at least one recurrent critical point. This estimate is optimal because the set of rational maps with all critical points non-recurrent is of full Hausdorff dimension. To cite this article: M. Aspenberg, J. Graczyk, C. R. Acad. Sci. Paris, Ser. I 347 (2009).     

Around Browder’s fixed point theorem for contractions

We revisit a fixed point theorem for contractions established by Felix Browder in 1968. We show that many definitions of contractive mappings which appeared in the literature after 1968 turn out to be equivalent formulations or even particular cases of Browder’s definition. We also discuss the problem of the existence of approximate fixed points of continuous mappings; in particular, we settle it in the affirmative for Browder contractions. Finally, we recall three problems concerning Browder contractions which remain unsolved. With great respect for Professor Felix E. Browder