Band 9, Heft 6

The modification of titania by metal / non metal ion doping, coupling with narrow band gap sensitizer, surface flourination, metal deposition, and together with recent ventures on application of {001} facets of anatase titania for visible light response with enhanced charge carrier separation are briefly overviewed.

A series of novel nitro-substituted ortho-analogs of POPOP was synthesized. Like the most of the other known compounds of this class, the synthesized molecules demonstrate high Stokes shift fluorescence emission owing to the planarization of their molecules at electronic excitation. Significant fluorescence quenching in polar solvents was described as the “energy gap law” action rather than the specific effect of the dialkylamino group excited state twisting.

The aim of this paper is to optimize and validate a high performance liquid chromatography (HPLC) method for separation and quantification of five isoflavones. A statistical central composite design was used to separate all peaks. These multivariate procedures were efficient in determining the optimal separation condition using resolution, capacity factor, asymmetry and number of theoretical plates. The effective separation of the examined compounds was applied on a Develosil RP Aqueous AR 5 RP-30 column with a gradient mobile phase system and a DAD detector. The isolation and preconcentration of the isoflavones from urine and plasma samples were conducted by means of the solid-phase extraction (SPE). For optimize SPE conditions various sorbents were tested. Furthermore, high recoveries and good relative standard deviations were obtained when the samples were passed through the Oasis HLB column. The developed method was validated and successfully applied for determination of isoflavones in urine and plasma.

This paper discusses the experimental results of the production of nanocolloidal silver using photoreduction method. Ultrafine crystalline gelatine-stabilised aqueous suspensions of silver bromide were used as a substrate for the synthesis of silver nanoparticles (Ag NPs). The influences of the reductant to substrate molar ratio, the medium’s pH, the type of the source of actinic radiation and the time of exposure to the efficient production of the Ag NPs were studied. A typical reaction was suggested, which involves the photo-induced reduction of silver bromide nanocrystals in the presence of ascorbic acid under specified physicochemical conditions. The properties of resultant silver particles were examined using UV-Vis spectroscopy and Dynamic Light Scattering (DLS). In addition, Transmission Electron Microscopy (TEM) was used for imaging the silver nanoparticle suspensions.

A homoleptic ethynyl-substituted ruthenium(II)-bisterpyridine complex representing a versatile synthon in supramolecular chemistry was synthesized and analyzed by NMR spectroscopy, mass spectrometry and X-ray diffractometry. Furthermore, its photophysical properties were detailed by UV/Vis absorption, emission and resonance Raman spectroscopy. In order to place the results obtained in the context of the vast family of ruthenium coordination compounds, two structurally related complexes were investigated accordingly. These reference compounds bear either no or an increased chromophore in the 4′-position. The spectroscopic investigations reveal a systematic bathochromic shift of the absorption and emission maximum upon increasing chromophore size. This bathochromic shift of the steady state spectra occurs hand in hand with increasing resonance Raman intensities upon excitation of the metal-to-ligand charge-transfer transition. The latter feature is accompanied by an increased excitation delocalization over the chromophore in the 4′-position of the terpyridine. Thus, the results presented allow for a detailed investigation of the electronic effects of the ethynyl substituent on the metal-to-ligand charge-transfer states in the synthon for click reactions leading to coordination polymers.

The oxidative catalytic degradation of the cationic dye methylene blue (MB) with NaOCl in aqueous solutions was studied using individual and iron modified Ni- and Co-oxide systems as catalysts. The adsorption extent and the contribution of the uncatalyzed oxidation on the overall degree of MB were determined. The results indicate that methylene blue—a representative of a class of dyestuffs resistant to biodegradation—could be successfully decolorized and degraded using nickel and cobalt oxide catalysts at room temperature. The highest catalytic activity manifests in the Co-oxide system which is consistent with the adsorption data. The oxidative degradation reaction proceeds via first-order kinetics. Temperature has a relatively small effect on the methylene blue degradation kinetics. The results obtained reveal that the catalysts investigated are suitable for oxidative destruction of methytlene blue dye in wastewaters.

The B3LYP/6-31G(d) simulations of competing CDA and HDA reactions between cyclopentadiene and (E)-2-arylnitroethenes prove that regardless of the medium polarity, the processes leading to respective 5-nitro-6-aryl-bicyclo-[2,2,0]-hept-2-enes 3,4 (paths A and B) should be most favoured, and the more electrophilic (E)-2-(p-nitrophenyl)-nitroethene should be more reactive than the less electrophilic (E)-2-(p-methoxyphenyl)-nitroethene. Asymmetry of the transition complexes on the favoured pathways increases with increase of medium polarity, but not sufficiently to enforce the zwitterionic mechanism. Analysis of competing pathways leading to HDA adducts proves that not all these compounds can be formed directly from the adducts. In particular, on the path C, the initially formed 5-nitro-6-aryl-bicyclo-[2,2,0]-hept-2-enes 3 is converted to 2-phenyl-4-aza-5-oxy-bicyclo-[3,4,0]-nona-3,7-diene N-oxides 5 as a result of a [3.3]-sigmatropic shift. On the paths D–F leading to 2-phenyl-4-aza-5-oxy-bicyclo-[3,4,0]-nonadienes N-oxides 6–8, the reaction proceeds according to a one-step mechanism.

A simple flow-based method was developed for the simultaneous separation of certain transition metal ions (Co, Ni, Cu, Zn, Cd) from aqueous systems, which ions show ecotoxic effects when present at elevated concentrations. A silica-gel-bonded macrocycle system, commonly known as molecular recognition technology (MRT) gel, was used for solid phase extraction (SPE) of the target analytes. The collection behavior of the MRT-SPE system was studied based on pH. Fortified deionized water samples containing 250 µg L−1 of each of the elements were treated at the flow rate of 1 mL min−1. The collected analytes were then eluted by 3 M HNO3 and analyzed using inductively coupled plasma spectrometry. Detection limits of the proposed technique were in the range of 0.004–0.040 µg L−1 for the studied metal ions. The validity of this separation technique was checked with spiked ‘real’ water samples, which produced satisfactory recoveries of 96–102%. The non-destructive nature and highly selective ion-extraction capability of the SPE material are the most important aspects of the proposed method and they are the main focus of this paper.

Microcomposites consisting of TiO2 (or Ce-doped TiO2) and ThO2 (0.5–2% of the TiO2 mass) are produced by sol-gel synthesis of TiO2 in presence of ThO2. X-ray diffraction study reveals the effects of ThO2 (compared to the ThO2-free TiO2, obtained by the same method) on the anatase interplanar distances, crystallites size and phase composition. The photocatalytic tests in presence of the composites under UV irradiation reveal an increase of the Malachite Green degradation rate constant. The effect depends on the Th relative content, temperature of annealing of the catalyst and addition of other doping agent. The highest photocatalytic activity is observed for TiO2 obtained at 550°C and containing 1% ThO2. The composite exhibits activity in dark, also. The presence of Ce4+ ions is not an obligatory requirement for the realization of the ThO2 effect. The reported results suggest that the radioactivity of the Th and/or its decay products is one of the main factors responsible for the increased photocatalytic activity of TiO2.

The aim of this study was to develop a method of manufacturing versatile hydrophobic coatings for polymers. Authors present a simple technique of polyurethane (PU) surface modification with covalently attached silicones (PDMS) or fluorocarbons (PFC). Diisocyanates were applied as linker molecules. The obtained coatings were characterized using spectroscopic analysis (FTIR), scanning acoustic microscopy (SAM) and water contact angle measurements. FTIR analysis revealed high efficiency of grafting reaction. The results of contact angle measurement indicated significant increase of hydrophobicity — from 66° (unmodified PU) to 113° (PU grafted with PDMS) and 118° (PU grafted with PFC). Acoustic microscopy analysis confirmed satisfactory homogeneity and smoothness of the fabricated layers. In vitro cell tests revealed non-adherent properties of the surfaces. Both, MTT assay and fluorescence staining confirmed non-cytotoxicity of the coatings, which makes them potential candidates for use in biomedical applications.

The influence of peptide sequence and Leu chirality in linear and cyclic peptides containing 3-[2-(9-anthryl)benzoxazol-5-yl]alanine on interaction with β-cyclodextrin were studied using fluorescence and NMR spectroscopy. The analysis of enthalpy-entropy compensation effect (α=1.05±0.02 and TΔS00=15.1±0.5 kJ mol−1) indicates that the entropic contribution connected with the solvent reorganization is the major factor governing the peptides-β-cyclodextrin complexation. Moreover, spatial orientation of guest-host molecule depends more than association constant on Leu residue configuration. However, the cyclization of the peptide chain substantially decrease the association constant with β-CD. An analysis of 2D NMR spectra reveals that inclusion complex is formed by penetration of cyclodextrin cavity from wider and narrow rims by anthryl group in the case of Box(Ant)-SPKL or anthryl and Leu residues for Box(Ant)-SPK(D)L analogue.

The NMR spectra of [2.2]paracyclophane with β- or γ-cyclodextrin in DMF-d7 at room temperature do not show significant complexation, while HPLC of the complexes in mixed H2O:alcohol solvents demonstrate complexation with different stoichiometries. At 243 K in DMF solution the H3 and H5 NMR signals of γ-cyclodextrin (but not β) exhibit complexation-induced chemical shifts denoting complex formation. According to HPLC, at room temperature the [2.2]paracyclophane complex with β-cyclodextrin in 20% H2O:EtOH exhibits 1:2 stoichiometry with K 1 = 1×102 ± 2, K 2 = 9.0×104 ± 2×103 (K = 9×106) while that with γ-cyclodextrin in 50% H2O:MeOH exhibits 1:1 stoichiometry with K 1 = 4×103 ± 150 M−1. Thermodynamic parameters for both complexes have been estimated from the retention time temperature dependence. For the β-cyclodextrin complexation at 25°C ΔG 0CD is −39.7 kJ mol−1 while ΔH 0CD and ΔS 0CD are −88.2 kJ mol−1 and −0.16 kJ mol−1 K−1. For γ-cyclodextrin, the corresponding values are ΔG 0CD = −20.5 kJ mol−1, ΔH 0CD = −33.5 kJ mol−1 and ΔS 0CD = −0.04 kJ mol−1 K−1.

This paper describes the preparation and characterization of poly(ethyl cyanoacrylate) colloidal particles loaded with the organic fluorophore Rhodamine 6G. We studied the physicochemical properties of the colloidal particles: morphology, size-distribution, ζ-potential, fluorescent properties and photobleaching upon UV-light illumination. The properties of the obtained colloidal particles, as well as the dye loading efficiency, were found to depend on the concentrations of ethyl cyanoacrylate monomer and Rhodamine 6G in the polymerization medium. The fluorophore release from the colloidal particles in aqueous buffer is also studied.

The modified BCR three-step sequential extraction procedure has been applied to two different samples of urban particulate matters (PM). The distribution of selected trace elements As, Cd, Cr, Mn, Ni, Pb, Zn was investigated and, in a comparative study, the presence of common organic air filters in extraction procedures was evaluated. Analytes in separate fractions were determined by ICP-OES and GFAAS, respectively, depending on concentration levels. While, due to air filters, a significant increase of some analytes mobility in individual fractions has been observed in case of the jet-milled PM (tunnel Letna), but in case of the PKC sample such effect was not found. The analyte impurities built in some filters has been tested, and the impact on the reliability of analyte results has been discussed. The arsenic species occurrence and their stability in presence of air filters (size 47 mm) were investigated in both urban PM samples as well, using HPLC-ICP-MS technique. Water soluble and by three-step BCR procedure extractable arsenic forms are shown in chromatograms

Polydimethylsiloxane nanoparticles were obtained by nanoprecipitation, using a siloxane surfactant as stabilizer. Two neural networks and a genetic algorithm were used to optimize this process, by minimizing the particle diameter and the polydispersity, finding in this way the optimum values for surfactant and polymer concentrations, and storage temperature. In order to improve the performance of the non-dominated sorting genetic algorithm, NSGA-II, a genetic operator was introduced in this study — the transposition operator — “real jumping genes”, resulting NSGA-II-RJG. It was implemented in original software and was applied to the multi-objective optimization of the polymeric nanoparticles synthesis with silicone surfactants. The multi-objective function of the algorithm included two fitness functions. One fitness function was calculated with a neural network modelling the variation of the particle diameter on the surfactant concentration, polymer concentration, and storage temperature, and the other was computed by a neural network modelling the dependence of polydispersity index on surfactant and polymer concentrations. The performance of the software program that implemented NSGA-II-RJG was highlighted by comparing it with the software implementation of NSGA-II. The results obtained from simulations showed that NSGA-II-RJG is able to find non-dominated solutions with a greater diversity and a faster convergence time than NSGA-II.

The crystal structure of 2-methylpyridinium tetrachloroferrate(III) was determined. The iron cation is tetracoordinated by chloride anions, and it adopts a slightly distorted tetrahedral coordination with three angles smaller, two almost equal and one larger than the tetrahedral. The compound is isostructural with its 3-, and 4-methylpyridinium analogues. The thermal properties of 2-, 3- and 4-methylpyridinium tetrachloroferrates(III) have been studied using TG and DSC techniques. The compounds exhibit a high stability in the melt.

A novel redox-active calix[4]arene-TTF 5 was prepared by the reaction of p-tert-butylcalix[4]arene 4 with the tosylated TTF 3 in the presence of cesium fluoride. The structure of the dyad 5 was identified by X-ray diffraction analysis, and the preliminary electrochemical properties of 5 were investigated by cyclic voltammetry (CV), for which two reversible one-electron waves were observed. Moreover, the UV-vis absorption spectra studies show that the dyad 5 undergoes progressive oxidation at the TTF moiety in presence of increasing amounts of Cu2+ or Hg2+.

The determination of mercury in fish typically involves analysis of muscles. For predicting the concentration of mercury in fish muscle on the basis of the analysis of fish scales or fins, the relationship between total mercury concentrations in fish muscles and in fish scales and fins was studied. Mercury content in fish muscles, scales and fins was determined by atomic absorption spectrometry with thermal decomposition of the sample in a flow of oxygen. A number of scale treatments were applied in order to remove impurities and to enhance the prediction quality. For scale treatment, 40 min of washing with DI water in an ultrasonic bath is recommended. A coefficient of determination r2= 0.93 for the relationship between Hg concentrations in muscles and scales was achieved for 40 fish among the different fish species tested (European bream, perch, roach) from the Hamry Reservoir, Czech Republic. With respect to fin sampling, the coefficient of determination r2 for these fish was 0.86. The analysis of fish scales and caudal fins is a useful screening tool for assessing the relative mercury contamination of monitored fish. The method of sampling scales is not suitable for fish species with small scales such as brown trout.

Amphiphilic macromolecular micelles are advantageous for drug delivery applications due to the decrease of side-effects, ease of screening drugs against degradation, long-term stability, targeted delivery and control of the amount of the released drug. A series of amphiphilic azo-polymers having a flexible or rigid main-chain were synthesized and characterized. The presence of chlorobenzyl side-groups allowed both the easy bonding of photo-sensitive or hydrophilic groups and good control of the degree of substitution. The chemical structure was confirmed by 1H-NMR. The critical concentration of aggregation (CCA) was calculated using the fluorescence emission spectrum of pyrene. The interest was focused on a preliminary study concerning the disaggregation capacity of micelles under UV irradiation. The presence of micellar aggregates was confirmed by DLS and SEM and different organization of the amphiphilic polymers was evidenced depending on polymers concentration and polymers structure. In low polymer concentrations in water predominantly globular aggregates were formed. The increase in concentration increased the polydispersity index due to the fusion of micelles and formation of associates of globular aggregates, inter-micellar associates (clusters) and vesicles.

Two new low-molecular weight compounds — (Z)-4-(4-(dimethylamino)benzylidene)-1-(9-ethyl-9H-carbazol-3-yl)-2-phenyl-1H-imidazol-5(4H)-one and 2-(6-hydroxyhexyl)-6-(pyrrolidin-1-yl)-1H-benzo[de]isoquinoline-1,3(2H)-dione) — with possible application in organic light-emitting devices were synthesized. Their photophysical properties in solution and in polymer films were investigated. The determined relative fluorescence quantum yields in solution for both compounds were 0.003 and 0.51, while those in poly(methyl methacrylate) films were around 0.10 and 1.0, respectively. For 1H-imidazol-5(4H)-one derivative, single-layer organic displays with one emitting layer were prepared by spin-coating technology. The applied voltage was 40 V (AC) with 1–3 KHz frequency. The emission maximum of the experimental AC display structures was at 600–630 nm. For displays with 2-(6-hydroxyhexyl)-6-(pyrrolidin-1-yl)-1H-benzo[de]isoquinoline-1,3(2H)-dione) the applied voltage was 60 V (AC) with 6-9 KHz frequency, but its future success will require more appropriate binding polymers. Based on the obtained experimental results, it is concluded that the investigated compounds could be applied for preparation of color electroluminescent structures.

The LaMg2Cu9, PrMg2Cu9, LaMg2Cu4Ni5, PrMg2Cu4Ni5 and TbMg2Cu6Ni3 alloys were prepared for the investigations of crystal structure, magnetic and hydrogen storage properties. The magnetic properties of several REMg2Cu9−xNix compounds have been studied up to 9 T and from 2 to 300 K. Tb compounds show a ferrimagnetic (with Ni) or antiferromagnetic (without Ni) behaviour, which can be attributed to the Tb magnetic structure. At high temperature a paramagnetic Curie Weiss behaviour is observed and the effective moment corresponds to that of Tb. A magnetic contribution of Pr moment is observed in both Pr compounds, with larger magnetization for PrMg2Cu4Ni5 and a transition at 3 K. The hydrogen absorption occurs at 95 bar for LaMg2Cu9 (3 H f.u.−1) and above 2 bars for LaMg2Cu4Ni5 (1.6 H f.u.−1). The effect of Cu-Ni substitution on the electrochemical properties of LaMg2M9 ternary alloys was investigated leading to maximum discharge capacity of 250–310 mAh g−1.

Complex formation and liquid-liquid extraction were studied in systems containing indium(III), 4-(2-pyridylazo)resorcinol (PAR), tetrazolium salt (TZS), water and chloroform. Two different TZS were used: 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT). The optimum conditions for extraction of In(III) as a ternary complex, (TT+)[In(PAR)2] or (MTT+)[In(PAR)2], were found: pH, extraction time, concentration of PAR and concentration of TZS. The constants of extraction (Kex), constants of association (β), constants of distribution (KD) and recovery factors (R%) were determined. The apparent molar absorptivities in chloroform were calculated to be ɛ′520=6.6×104 L mol−1 cm−1 and ɛ′515=7.1×104 L mol−1 cm−1 for the systems with TTC (I) and MTT (II), respectively. Beer’s law was obeyed for In(III) concentrations up to 3.4 µg mL−1 in both the cases. The limits of detection (LOD=0.07 µg mL−1I and LOD=0.12 µg mL−1II), limits of quantification (LOQ=0.24 µg mL−1I and LOQ=0.41 µg mL−1II) and Sandell’s sensitivities (SS) were estimated as well.

This study examined the direct spectrometric method for determining non-ionic surfactants in highly-polluted samples (i.e., soil leachates) containing high concentrations of humic acids. Meso-tetra-(3,5-dibromo-4-hydrooxyphenyl)-porphyrin served as a coloration agent. The method was tested by use of two polyethoxylate/polypropoxylate — based non-ionic surfactants: Triton CF-21 containing aromatic groups in the structure and Novanik 1047A containing only linear hydrocarbon chains. The main goal was to quantify the influence of interfering species to the results. A test for coincidence of regression lines was employed for objective evaluation of the humic acid influence on the determination. It was observed that for linear surfactant Novanik 1047 A the method provides reliable result and thus, can serve for routine analyses. Regarding Triton CF-21, an interfering effect of humic acids was observed; however, after sufficient dilution of the samples, the method can be used as well. Finally, the method can be used for simple analyses of problematic samples without complicated sample-pretreatment.