Band 68, Heft 11

The ability of MALDI TOF MS (matrix-assisted laser desorption ionisation time-of-flight mass spectrometry) to identify cultivable microflora from two waste disposal sites from non-ferrous metal industry was analysed. Despite the harsh conditions (extreme pH values and heavy metal content in red mud disposal site from aluminium production or high heavy metal content in nickel sludge), relatively high numbers of bacteria were recovered. In both environments, the bacterial community was dominated by Gram-positive bacteria, especially by actinobacteria. High-quality MALDI TOF mass spectra were obtained but most of the bacteria isolates could be not identified using MALDI Biotyper software. The overall identification rate was lower than 20 %; in two of the environments tested identification rates were lower than 10 %. As a dominant bacterial species, Microbacterium spp. in drainage water from an aluminium red mud disposal site near Žiar nad Hronom, Bacillus spp. in red mud samples from the same site, and Arthrobacter spp. from nickel smelter sludge near Sereï were identified by a combination of the Biolog system and 16S rRNA sequence analysis. As the primary focus of the MALDI TOF MS-based methodology is directed towards medically important bacteria, reference database spectra expansion and refinement are needed to improve the ability of MALDI TOF MS to identify environmental bacteria, especially those from extreme environments.

A few non-conventional humate sorbents, i.e. iron humate (FeH), aluminium humate (AlH), calcium humate (CaH), magnesium humate (MgH), and zinc humate (ZnH), were prepared from a commercial product Fortehum L/K (Humatex, Bílina, Czech Republic). The metal content in humates was determined by X-ray fluorescence analysis, the organic elements (C, H, N, and S) were analysed by an Elementar Vario III and the functional groups were determined by classical methods using KBr pellets and diffuse reflection infrared spectroscopy (DRIFTS). FeH, AlH, and ZnH were tested as sorbents for the removal of inorganic or organic pollutants (metals, inorganic ions, dyes, and chlorophenols) from waste water. Sorption properties decreased in order: ZnH, AlH, FeH. CaH and MgH are partly soluble and therefore they are not usable as sorbents. However, their ion-exchange abilities for heavy metals are excellent which makes them usable for phytoremediation and bioremediation.

The main aim of the presented work was to design and characterize the rhizofiltration system comprised of giant reed plants (Arundo donax L.), as species with phytoremediation potential, for the removal of cadmium as a toxic metal and zinc as an important microelement from model solutions spiked with radionuclides 109Cd and 65Zn. The possibility of effective cadmium and zinc rhizofiltration by the root system of giant reed plants under continuous flow conditions to achieve complete decontamination was confirmed. The highest 109Cd and 65Zn specific radioactivity (Bq g−1; dry mass) was found in case of plants located near the input of the solution into the system, whereby the radioactivity in the plants decreased in the direction of the solution flow within the system. On the other hand, gradual increasing of the concentration ratio [Cd]shoot: [Cd]root within this horizontal plants location was observed. Individual experiments showed that the efficiency of cadmium rhizofiltration decreased in the order of model solutions: synthetic wastewater (χ = 505 μS cm−1), deionized water (χ = 29.6 μS cm−1), 100 % Hoagland medium (χ = 1675 μS cm−1). The same results were also found in case of zinc rhizofiltration. For the description of cadmium and zinc rhizofiltration processes, the kinetic mathematical models widely applied for sorption processes under continuous flow conditions were successfully used.

The aim of the presented work was to evaluate the uptake and distribution of 2-fluoro-2-deoxy-d-glucose spiked with 18F (2-[18F]FDG) in tissues of tobacco plants (Nicotiana tabacum L.) by positron emission tomography and multivariate data analysis after the immersion of the petiole of excised leaf or root of a tobacco plant in a glucose solution. From individual experiments it was found that increasing glucose concentration (c glu) in the applied solution resulted in significantly higher 2-[18F]FDG diffusion and translocation within the leaf parenchyma. More than a four times increase of the 2-[18F]FDG translocation into the aboveground parts of the tobacco plant in case of the root immersion in solution with 100-times higher c glu in comparison with the control (c glu = 0.00762 mg cm−3) was determined. These facts were not confirmed only visually on basis of the obtained 3D images, but also by the increasing coincidence transfer factor (TFc) values defined by the ratio of the number of analyzed coincidences in the non-immersed parts of leaf or plant to coincidences in leaf petiole or root immersed in the solution. Cluster and principal component analysis suggest that the 2-[18F]FDG uptake by the petiole of excised leaf and root system was realized by different mechanisms; also, the 3D image quality is influenced by the initial radioactivity of the applied solution.

The excessive application of organophosphate pesticides (OPPs) in crop fields close to hives and its application in beekeeping practices are potential sources of contamination of propolis. Pesticides were extracted from raw propolis by matrix solid-phase dispersion. Because of the complex chemical composition of propolis, binary solvent mixtures based on acetonitrile and a relatively non-polar solvent in different proportions were tested for the selective elution of OPPs. The effect of mixed solvents on clean-up was evaluated by GC-MS and the main interfering compounds co-eluted with pesticides were identified. In addition, three volumes of the solvent mixture and the volume of the sample were evaluated in an experimental factorial design. The final experimental conditions were 1 mL of dissolved propolis and 8 mL of acetonitrile/dichloromethane (g4 r = 25: 75). Mean recoveries ranged from 55 % to 96 % (relative standard deviation < 8 %) with an inter-day precision lower than 24 %. The proposed method was applied to the analysis of real samples obtained from local beekeepers.

A method for the rapid and sensitive determination of peroxyacetyl nitrate (PAN) in air based on a chemiluminescence reaction with an alkaline solution of luminol in the chemiluminescence aerosol detector is described. The PAN is chromatographically separated from nitrogen dioxide and ozone in a packed column filled with 5 % OV-1 on Chromosorb 30/60 and the eluted PAN is detected via the direct reaction with the luminol solution consisting of 0.002 mol L−1 luminol, 1 vol. % Brij-35 and 0.1 mol L−1 KOH. The limit of detection is 14.9 ng m−3 (3 ppt) of PAN. Alternatively, the PAN after separation is thermally converted to NO2 which is detected by the chemiluminescence reaction with a solution consisting of 0.002 mol L−1 luminol, 0.5 mol L−1 KOH, 0.2 mol L−1 Na2SO3, 0.1 mol L−1 KI, 0.05 mol L−1 EDTA and 0.5 vol. % triton X-100. The alternative approach affords the simultaneous determination of PAN and NO2. The limit of detection is 50 ppt of PAN and 50 ppt of NO2. The time resolution is 3 min. The method was applied to the measurement of ambient peroxyacetyl nitrate in air.

The decolorisation process of a synthetic textile dye, direct violet 51, was investigated in an aqueous solution using an electrochemical method in a batch electrochemical cell. Graphite electrodes were used as the anode and cathode for the decolorisation process. The parameters such as applied current, initial pH, solution conductivity, interfering ions, and effect of electrodes were optimised. It was found that the dye with an initial concentration of 20 mg L−1 could be removed after 50 min using a current of 100 mA with colour removal of up to 94 %. The UV-VIS spectra of the dye were analysed prior to and after treatment and these confirmed that the conjugated systems were decomposed at a current of 100 mA. The optimised method was successfully applied to real wastewater samples.

A simple and fast analytical method for the determination of the main steroidal glycoalkaloids, α-chaconine and α-solanine, in commercial potato crisps, based on QuEChERS (Quick, Easy, Cheap, Effective, Rugged, Safe) extraction and ultra performance liquid chromatography coupled with an electrospray ionization triple-quadrupole tandem mass spectrometer (UPLC-MS/MS) in the multiple reaction monitoring mode was established and validated. The sample preparation procedure involves the extraction of the analytes with acidified acetonitrile and simultaneous liquid-liquid partitioning achieved by an addition of anhydrous magnesium sulfate and sodium acetate without any further clean-up steps. The limits of quantification (LOQs) for α-chaconine and α-solanine were 31 μg kg−1 and 16 μg kg−1 of fresh mass, respectively, at the signal-to-noise ratio (S/Ns) of 10. The method was applied in a survey of the content of α-chaconine and α-solanine in twenty commercial potato crisps from different brands. The results showed that all the products contained α-chaconine and α-solanine in widely varying concentrations. The amount of α-chaconine was higher than that of α-solanine in all samples.

An ultrasensitive polyclonal antiserum against ciprofloxacin (CPFX) was developed by introducing cationized bovine serum albumin (BSA) as the carrier. Conjugates used as immunogens were synthesized using CPFX coupled to BSA cationized with ethylenediamine and hexamethylenediamine, namely CPFX-eBSA and CPFX-hBSA. The results showed that the antisera immunized with CPFX-hBSA exhibit an improved sensitivity and specificity compared with those immunized with CPFX-eBSA. Under the conditions of optimal heterologous enzyme-linked immunosorbent assay, the optimal antiserum yielded an IC50 of 0.097 ng mL−1, which proves it to be more sensitive than any CPFX antibody. Cross-reactivities with norfloxacin, enrofloxacin, and ofloxacin were < 3.0 %. No cross-reactivities with penicillin and gentamicin were found. The limit of detection was 0.01 ng mL−1, which is far below the maximum residue level established by the EU regulation, suggesting the great potential of the presented antiserum for quantitative assays of CPFX in samples.

In this study, laccase (from Trametes versicolor, 8.3 U mgenz−1) was used for the decolorisation of Saturn Blue L4G (10 mg L−1). The efficiency of the decolorisation (ratio between the amount of decolorised dye and initial amount of dye) by a free enzyme was 48 % and the decolorisation rate was determined at 2.11 × 10−3 mgdye mgenz−1 min−1. After immobilisation in lens-shaped poly(vinyl alcohol) hydrogel capsules LentiKats® Biocatalyst (LB) (concentration of immobilised enzyme: 4 mg per g of particles; volume-loading rate of LB: 10 g per 100 mL of medium), the enzyme retained 16.1 % of its original activity (1.34 U mgenz−1). Immobilised laccase was used for the dye decolorisation in 130 repeated batch tests with 71 % efficiency (LB activity: 7 × 10−3 mgdye min−1 gLB−1). In continuous mode (after 716.5 h), the efficiency of the dye decolorisation was 48 % (LB activity: 3.3 × 10−4 mgdye min/−1 gLB−1).

A high-efficient purification method of flavonoids from Lithocarpus polystachyus Rehd leaves is reported. Two adsorbents functionalized with glucosamine (GA) and β-cyclodextrin (β-CD) were synthesized and characterized by the Fourier transform infrared (FTIR) spectra. Also, adsorption properties and purification effect of flavonoids on different adsorbents were investigated. Two typical commercial adsorbents, AB-8 and D101, were employed as the reference materials. The adsorption capacity was enhanced remarkably by the introduction of GA and β-CD groups to the adsorbents. Moreover, the isotherms were well fitted by the Freundlich model. After a one-step column chromatographic separation, the purity of phloridzin increased significantly from 14.65 % to 79.48 % for PS-CD, to 66.56 % for PS-GA, 44.68 % for D101, and to 52.84 % for AB-8. This study provides a novel alternative matrix for the purification of phloridzin from Lithocarpus polystachyus Rehd leaves extracts.

A novel nickel metallodendrimer was synthesized with poly(amidoamine), 3,5-di-tert-butyl-2-hydroxy-benzaldehyde and nickel chloride via the Schiff’s base and the complexation reactions. Structures of the dendritic ligand and its nickel complex were characterized by IR, NMR, UV, ESI-MS and elemental analyses. This new nickel metallodendrimer as a catalyst precursor, together with methylaluminoxane as an activator, was evaluated in the ethylene oligomerization. Under the conditions of 0.5 h, 0.5 MPa, 25°C and Al/Ni mole ratio 500: 1 employed for the nickel complex, the catalytic activity showed a maximum value of 4.93 × 105 grams per mole of Ni catalyst per hour. Substituents on the benzene ring seem to have a negative influence on the catalytic activity of the complex.

An alcohol/salt-based aqueous two-phase system (ATPS) was employed for enantioseparation of (R,S)-mandelic acid (MA) and (R,S)-α-cyclohexylmandelic acid (α-CHMA). Sulfonated β-cyclodextrin (Sf-β-CD) with different degrees of substitution (DS) was considered as the chiral selector. The ethanol/(NH4)2SO4 system showed the optimal chiral recognition ability for MA. To optimize the experimental conditions, Sf-β-CD concentration, ethanol and salt concentration, temperature, and pH were studied. The recognition ability of enantiomers was mainly dependent on the type of the chiral selector but the ethanol and (NH4)2SO4 concentrations also had significant influence on the enantiomeric recognition. The maximum values of α and ee up of 1.69 and 16.3 % were obtained, respectively, for MA under the optimal conditions. A potential application of this alcohol/salt ATPS is the scale-up of chiral separation of MA.

The main impetus for utilising the biosludge from the neutral sulphite semi-chemical pulping process is the Finnish legislation which from 1st January 2016 prohibits the deposition of this residue in landfills in Finland. The dry matter content of the biosludge in this case study was low (12.1 mass %), meaning that incineration of this residue is uneconomical. The biosludge was rich in P (6260 mg kg−1). This, together with the high total organic carbon value of 459 g kg−1 and the metal concentrations (As, Cd, Cr, Cu, Ni, Pb, Zn and Hg) lower than the Finnish permissible limits for land application, supports wide and various end-uses for this residue. Except for S (27600 mg kg−1) and Cd (1.4 mg kg−1), the other heavy metal concentrations in the biosludge were lower than the maximum values for heavy metal concentrations in a non-contaminated soil referred to the literature. From the utilisation perspective, and in view of the high levels of S and Na, this residue could efficiently be used, for example, to landscape landfills.

This study is aimed at atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) using a novel catalyst. The bis-(2-dodecylsulfanyl-ethyl)-amine (SNS) tridentate ligand with mixed donor atoms was synthesized in high purity using inexpensive reagents and was reacted with copper(I) bromide to produce the CuBr/SNS catalyst. The catalyst mediated living polymerization of MMA yielding polymers with controlled molecular masses and narrow molecular mass distributions (PDI < 1.25). Also, the kinetic plot exhibited a linear increase of ln([M]0/[M]) versus time, indicating constant concentration of propagating radicals during the polymerization. The products were characterized by 1H NMR, 13C NMR, FT-IR, UV-VIS, GC and elemental analyses (CHNS) and by GPC.

UV-cured caprolactone-based polyurethane acrylate (PUA) polymer blend electrolytes were prepared and characterised. To develop polymer electrolytes suited to ambient temperature, an ionically-conductive and reliable polymer electrolyte based on urethane acrylate resins synthesised from a fluorine-containing di-functional oligomer 6F ethoxylated diacrylate, a di-functional reactive diluent 1,6-hexanediol diacrylate for adjusting the viscosity, and a radical photo-initiator doped with a mixture of lithium salts were used. Free-standing flexible electrolyte films were prepared by UV-curing via free-radical photopolymerisation. The performance of the lithium polymer cell system (Li/PE(F4)/LiCoO2) was determined by electrochemical impedance spectroscopy, cyclic voltammetry, a galvanostatic recurrent differential pulse, chronocoulometry and chronoamperometry. The electrolyte with optimal amounts of fluorine-containing oligomer and optimal salt mixture content exhibited enhanced conductivity, showing a conductivity of 1.00 × 10−4 S cm−1 at ambient temperature. The specific capacity, specific energy and specific power of a Li/PE(F4)/LiCoO2 cell were also determined.

Cobalt ion (Co2+)-doped polyaniline (PANI-Co), poly(N-methylaniline) (PNMA-Co), and poly(N-ethylaniline) (PNEA-Co) films were synthesised electrochemically on a pencil graphite electrode (PGE) and their electrochemical properties were investigated for supercapacitor applications. The polymer film-coated electrodes (PGE/PANI-Co, PGE/PNMA-Co, and PGE/PNEA-Co) thus obtained were characterised by scanning electron microscopy (SEM) and different electrochemical methods. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were employed in 0.1 M H2SO4 solution to calculate the specific capacitance (C S) values of the electrodes. The maximum C S of 192.94 F g−1, 139.83 F g−1, and 47.12 F g−1 were achieved for PGE/PANI-Co, PGE/PNMA-Co, and PGE/PNEA-Co at 1 mV s−1, respectively. On the other hand, the charge/discharge stability of the electrodes was analysed using the repeating chronopotentiometry (RCP) method. The RCP measurements indicate that the electrodes could be used as an electrode active material for low voltage supercapacitor applications.

At present, inorganic semiconducting materials are the most economical and viable source for the renewable energy industry. The present work deals with the morphological and optical characterization of copper oxide (CuO) and zinc oxide (ZnO) thin films fabricated by layer by layer deposition on nickel oxide (NiO) coated indium tin oxide (ITO) glass by solution processing methods, mainly chemical bath deposition (CBD) and hydrothermal deposition (HTD) processes at room temperature. As a whole, the above inorganic composite materials (NiO/CuO/ZnO) can be applied in photovoltaic cells. An attempt has been made to study structural, morphological and absorption characteristics of NiO/CuO/ZnO heterojunction using state of the art techniques like X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV spectroscopy. The energy band gaps of CuO and ZnO have also been calculated and discussed based on the UV spectroscopy measurements.

A simple and efficient procedure for the synthesis of 14-aryl-14H-dibenzo[a,j]xanthene derivatives through one-pot condensation of 2-naphthol with aryl aldehydes in the presence of niobium pentachloride is described. The reactions were carried out using 25 mole % of NbCl5, at ambient temperature, and in acceptable reaction times, affording excellent yields of the products.

Biguanides are a class of drugs derived from biguanide and they are the most widely used drugs for diabetes mellitus or pre-diabetes treatment. An investigation of their interaction and a transport protein such as β-lactoglobulin (BLG) at atomic level could be a valuable factor in controlling their transport to biological sites. Molecular-docking and molecular dynamics simulation methods were used to study the interaction of metformin, phenformin and buformin as biguanides and BLG as transport protein. The molecular-docking results revealed that these biguanides bind to BLG and that the BLG affinity for binding the biguanides decreases in the following order: phenformin — buformin — metformin. The docking results also show the hydrophobic interactions to have a significant role in the BLG-biguanides complex stability. Analysis of molecular dynamic simulation trajectories shows that the root mean square deviation of various systems attained equilibrium and fluctuated around the mean value at various times. The time evolution of the radius of gyration and the total solvent-accessible surface of the protein showed that BLG and BLG-biguanide complexes became stable at approximately 2500 ps and that there was not any conformational change in the BLG-biguanide complexes. In addition, the profiles of atomic fluctuations show the rigidity of the ligand-binding site during the simulation.

The current work is a study of the conformational space of the non-ionic N-formylmethionine molecule around its seven structurally significant internal backbone torsional angles at B3LYP/6-31++G(d,p) levels of theory in the gaseous phase. The potential energy surface exploration reveals that a total of 432 different conformers would result if all the possible combinations of the internal rotations were to be considered. A set of twelve conformers of the N-formylmethionine molecule are then further analysed in terms of their relative stabilities, theoretically predicted harmonic vibrational frequencies, HOMO-LUMO energy gaps, ESP charges, rotational constants and dipole moments calculated using MP2/6-31++G(d,p) and B3LYP/6-311++G(d,p) levels. The calculated relative energy-range of the conformers at the MP2 level is 11.08 kcal mol−1 (1 kcal = 4.1868 kJ), whereas the same obtained at the B3LYP level is 10.02 kcal mol−1. The results of this study provide a good account of the role of four types of intramolecular H-bonds, namely O…H—O, O…H—N, O…H—C and N…H—C, in influencing the energies of the conformers as well as their conformational and vibrational spectroscopic aspects. The relative stability order of the conformers appears to depend on the level of theory used while the vibrational frequencies calculated at the B3LYP level are in better agreement with the experimental values.