Band 5, Heft 4

Poly(9,9-dioctylfluorene) (PFO) shows highly efficient blue emission with photo excitation occurring between 340–400 nm. Here we show that PFO can in dilute solution emit at a wavelength well below that at which it is being exited. This, we propose is related to an energy transfer from conjugated parts of the polymer chain into more localised states which then emit at a lower wavelength. These localised states can be considered as defects in the conjugation of the polymer or as chain ends. These may produce quasi monomer or quasi dimer species within the chain, which will have a HOMO-LUMO gap of higher energy than the conjugated polymer. These then fluoresce at the lower wavelength; essentially causing, by energy transfer, a process of energy up-conversion.

The corrosion properties of the passive layers formed on iron-nickel-chromium electrodeposits of Fe29Ni51Cr20 were investigated in 0.3 M borate solution at a‘ pH of 8.4. On the basis of measurements by cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy, a low passive dissolution/corrosion rate was identified for the electrodeposited Fe-Ni-Cr alloys due to the nature of the established corrosion layer. The stability of this passive layer was further enhanced after corrosion under oxidizing conditions. Mössbauer spectroscopic measurements confirmed the existence of a thin passive layer on the amorphous electrodeposits.

Interaction of red blood cells (RBCs) with unmodified and partially (50%) silylated fumed silica A-300 (nanosilica)was studied by microscopic, XRD and thermally stimulated depolarisation current (TSDC) methods. Nanosilica at a low concentration C A-300C A-300 = 1 wt% all RBCs transform into shadow corpuscles because of 100% haemolysis. Partial (one-half) hydrophobization of nanosilica leads to reduction of the haemolytic effect in comparison with unmodified silica at the same concentrations. A certain portion of the TSDC spectra of the buffered suspensions with RBC/A-300 is independent of the amounts of silica. However, significant portions of the low-and high-temperature TSDC bands have a lower intensity at C A-300 = 1 wt% than that for RBCs alone or RBC/A-300 at C A-300 = 0.01 wt.% because of structural changes in RBCs. Results of microscopic and XRD investigations and calculations using the TSDC-and NMR-cryoporometry suggest that the intracellular structures in RBCs (both organic and aqueous components) depend on nanosilica concentration in the suspension.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) and thin-layer chromatography (TLC) have been used to study dopamine and iron mediated free-radical transformation of lipids in their hydrophilic parts. It has been shown that the action of the dopamine/Fe2+ system on galactocerebroside or cardiolipin, which are the components of mixed micelles, results in formation of ceramide or phosphatidic acid and phosphatidylhydroxyacetone, respectively. These data, when combined with results obtained using the ascorbate/Fe2+/H2O2 oxidizing system with the same substrates, demonstrate that the formation of these products proceeds via an OH-radical induced fragmentation taking place in polar moiety of the starting lipids.

This paper presents the syntheses, characterization and photochromic behavior of some new azo-polysiloxanes modified with uracil, cytosine or nitro-phenolic groups. Taking into consideration the possibility of generating H-bonds or donor/acceptor interactions, this class of materials present a potential applicability in the immobilization of biomolecules and their nano-manipulations. Also, such compounds are capable of producing a fluid phase, with directional flowing capacity. For all these polymers, the molecular modeling simulations have shown disordered structures, which would generate amorphous phases, a very important aspect for molecules’ nano-manipulation. The photochromic behavior in the presence of UV irradiation was also evaluated.

New hydrazones of 2-(5-thioxo-4,5-dihydro-1,3,4-thiadiazol-2-ylthio)acetohydrazide have been obtained and the percentages of anti/syn - conformers were determined. Based on the analyses of 1H NMR spectra, it was concluded that for hydrazones obtained from the 2- hydroxybenzaldehydes and 2’-hydroxycetophenones the ratio between the anti-and syn-conformers depends on the strength of intramolecular hydrogen bond (IMHB) between the nitrogen atom of the imino group and the proton of the 2-hydroxy group. It was shown that increase in IMHB strength results in stabilization of the anti-conformer in solution.

In this work we present the results of high level ab initio calculations on weakly bound complexes of aluminium trichloride and hydrogen halides, HX, halogens, X2 and diatomic interhalogens, XY (where X, Y = F, Cl, Br). Based upon these calculations we have predicted that all structures in the staggered conformation (except for Cl3AlFH and Cl3AlClH) are stable minima while those in the eclipsed configurations are transition state structures. In the XH complexes the strength of interaction with the Cl3Al group is FH > ClH > BrH. In the case of X2 species it is Br2 > F2 > Cl2, and finally in the XY (YX) group it is: FBr > ClBr > FCl > BrCl > BrF > ClF.

Activated diffusion of water between macromolecules in swollen cellulose is accompanied by anomalously high kinetic isotope effects of oxygen. The separation factor of heavy-oxygen water (H218O /H216O) is thousands of permilles instead of tens of permilles according to modern Absolute Rate Theory. This anomalous separation under usual conditions is disguised by the opposing process of very fast equalization to equilibrium through water-filled cellulose pores. This process is quicker by approximately 3 orders of magnitude than diffusion through the cellulose body. As a consequence, this opposition-directed equalization virtually eliminates the results of isotope separation. To reveal this anomaly it is necessary to suppress equalization, which was the primary problem for both discovery of this anomaly and its investigation. The method of investigating the anomalous separation in cellulose was developed with suppression of this negative influence. Discussion of the theoretical nature of the anomalous kinetic isotope effect is presented. This theoretical study would probably permit the discovery and use for isotope separation of the anomalously high isotope effect for other chemical elements, in particular, for those heavier than oxygen.

A series of novel cyclic urea molecules 5,6-dihydroxy-1,3-diazepane-2,4,7-trione as HIV-1 protease inhibitors were designed using computational techniques. The designed molecules were compared with the known cyclic urea molecules by performing docking studies, calculating their ADME (Absorption, Distribution, Metabolism, and Excretion) properties and protein ligand interaction energy. These novel molecules were designed by substituting the P 1/P′ 1 positions (4th and 7th position of 1, 3-diazepan-2-one) with double bonded oxygens. This reduces the molecular weight and increases the bioavailability, indicating better ADME properties. The docking studies showed good binding affinity towards HIV-1 protease. The biological activity of these inhibitors were predicted by a model equation generated by the regression analysis between biological activity (log 1/K i ) of known inhibitors and their protein ligand interaction energy. The synthetic studies are in progress.

Ionic liquid-functionalized mesoporous materials exhibited high catalytic activity in versatile organic reactions, such as cycloaddition of carbon dioxide (CO2) with epoxide, aza-Michael addition of amines to α, β-unsaturated carbonyl compounds, and the Biginelli reaction of aldehyde, ethyl acetoacetate and urea. Recycling of the catalyst in these reactions could be carried out and the catalyst used at least five times without significant loss in activity.

In the last decade, different methods have been developed for the determination of chromium(VI) concentration in water. These methods use high cost equipment or they require a long preparation time. Because of their drawbacks, this paper describes an on-line, rapid and sensitive procedure for the determination of Cr(VI) concentrations in aqueous solutions via pH and absorption measurements. Only four Cr(VI) species are considered. The effects of pH and of total amount of chromium on the Cr(VI) speciation are investigated. The molar absorptivities of four chromium species at 371 nm are determined by minimising an objective function. The knowledge of these molar absorptivities and the measurements of pH and absorption at 371 nm lead to a rapid determination of total Cr(VI) concentration. The reliability and applicability of the method were confirmed using synthetic water samples.

In the present paper QSAR modeling using electrotopological state atom (E-state) parameters has been attempted to determine the antiradical and the antioxidant activities of flavonoids in two model systems reported by Burda et al. (2001). The antiradical property of a methanolic solution of 1, 1-diphenyl-2-picrylhydrazyl (DPPH) and the antioxidant activity of flavonoids in a β-carotenelinoleic acid were the two model systems studied. Different statistical tools used in this communication are stepwise regression analysis, multiple linear regressions with factor analysis as the preprocessing step for variable selection (FA-MLR) and partial least squares analysis (PLS). In both the activities the best equation is obtained from stepwise regression analysis, considering, both equation statistics and predictive ability (antiradical activity: R 2 = 0.927, Q2 = 0.871 and antioxidant activity: R 2 = 0.901, Q2 = 0.841).

Electrochemical determination of dopamine (DA) in the presence of ascorbic acid (AA) was achieved on boron-doped diamond (BDD) film electrode by differential pulse voltammetry. The experimental results indicated that the oxidative peaks of DA and AA could be separated completely on anodically-treated (BDD) electrode without further modification, although these two peaks can not be separated on glassy carbon electrode. The peak separation of DA and AA was developed to be 0.44 V. High sensitivity was obtained to determine DA selectively with the coexisting of a large excess of AA in acidic media by DPV. The detection limit of DA was achieved to be 1.1 × 10-6 M in the presence of AA with the concentration of 200 times more than DA. This technique was also applied to the determination of DA in real samples.

Hybrid separation processes are becoming more and more important in the practice if membrane technologies are also involved. In this work, a systematic investigation is completed for three sequence alternatives of distillation and pervaporation. These are the following: pervaporation followed with distillation (PV+D), distillation followed with pervaporation (D+PV), two distillation columns and a pervaporation unit between them (D+PV+D). The hybrid separation process alternatives are evaluated with rigorous modelling tools, but first, a rigorous simulation algorithm is determined for the pervaporation. The three hybrid separation processes are rigorously modelled with CHEMCAD, and optimized with the dynamic programming optimization method for the case of the separation of ethanol-water mixture. The objective function is the total annual cost (TAC). The energy consumption is also investigated. The selection of the ethanol-water mixture has two motivations: (i) it is quite often studied and well known, and (ii) to make biofuel (ethanol) production more economical, membrane technologies might also be applied. The results are compared with each other and with the classical separation completed with heteroazeotropic distillation. The optimized TAC shows that the distillation column followed with pervaporation is the most economical hybrid separation process alternative. Its TAC is about 66% of that of the classical separation.

Pb, Mg and Ca were simultaneously determined in plant roots by slurry introduction into inductively coupled plasma optical emission spectrometry (SS-ICP-OES). Slurries were prepared in 0.5% or 5% (v/v) HNO3 with 0.5, or 5% (v/v) Triton X-100. Omission of the Triton X-100 improved results. Compared with wet ashing of the root sample followed by ICP-OES, ICP-MS and FAAS, the method offers: comparable results, simplification of sample preparation, less sample contamination, and reduction in the use of dangerous and corrosive reagents. The precisions varied: 1.7% for Mg, 2.8% for Ca and 4.3% for Pb, and were not significantly different (95% confidence level) from those of conventional analysis.

The original version of the article was published in Cent. Eur. J. Chem., Vol. 5(2), (2007), pp. 385–395. It can be also found online at: http://dx.doi.org/10.2478/s11532-007-0017-9. Unfortunately, the original version of this article contains mistakes in the Acknowledgements section. There should be: This work was supported by Grants 240/08/0016 of Institute of Chemical Technology, 257 Prague, 104/06/1079 of Czech Science Foundation and MSM6046137308 of Ministry of Education, Youth and Sports of the Czech Republic.