Band 65, Heft 5

In the present study, pervaporation was applied to the determination of tetrachloroethene (PCE) and dichloromethane (DCM) in liquid samples. PCE is the most commonly used solvent in drycleaning processes. PCE belongs to group 2A of carcinogens (probably carcinogenic to humans) according to the classification of the International Agency for Research on Cancer (IARC). DCM is also widely used as an industrial solvent for the purification and isolation of intermediates or products. DCM is classified as a “possible” human carcinogen by the IARC. The aim of this study was to evaluate a new procedure for the determination of DCM and PCE in liquid samples based on the pervaporative removal of DCM and PCE from liquid samples as an analyte isolation/enrichment technique, followed by a direct aqueous injection of the extracts onto the column of a gas chromatograph equipped with an electron capture detector (DAI-GC-ECD). The basic parameters of the new PV-DAI-GC-ECD procedure were evaluated.

A model of diffusive transport of benzoic acid through a liquid membrane (LM) separating two aqueous solutions, based on diffusion layers and the assumption of a steady state, has been developed and tested using experimental results. It has been found that a model with the apparent partition coefficient dependent on the concentration is able to describe the time dependence of acid concentration in LM with and without a maximum on that dependence. The quality of the model fit with the single apparent diffusion coefficient of benzoic acid is the same as the one which takes into account the diffusion of benzoic acid in different forms (undissociated and dissociated form in aqueous phase, monomer and dimer in organic phase); however, in the second case, the model becomes overparameterized. Assuming that the partition and diffusion coefficients are constant, the diffusion layer model corresponds to the model of reversible consecutive reactions. Analytical solution for such case is given. Apart from the partition equilibrium, also kinetics of partitioning was considered. It was shown that in some basic situations both cases yield identical results.

Oily wastewaters are produced in large amounts in many fields of food, mechanical, and other types of industry. In order to protect the environment, wastewaters must not be discharged directly into sewers. First, they must be cleaned at least down to 50 mg L−1 of oil content (according to Hungarian standard). In previous research, the authors found that oil-in-water emulsions can be separated with filtration using ceramic ultrafiltration tubular membranes. The relatively high price of ceramic membranes can be compensated by the fact that this separation process can be significantly intensified by static mixers inside the tubular membranes. New generations of ceramic membranes are the ceramic capillary membranes. These two different types of membranes and their effects on permeate flux, oil retention and specific energy consumption were compared in this work. The results, obtained with a stable oil-in-water emulsion as feed, showed that the use of novel ceramic capillary membranes at optimal operating cross-flow rate and transmembrane pressure is reasonable. The results have also shown the advantage of static mixing in the lumen side of the membrane tube providing a wider range of satisfactory separation level and increased permeate flux.

A promising new process for the regeneration of solvents with ionic liquid by molecular distillation has been proposed. The main advantage of this process compared with the classic stripping of acids with alkali solution is that the volatile organic acid is recovered with a yield of about 88 % in the form of free acid, not as its salt. Furthermore, improvement on the yield of the stripping can be assumed. The consumption of chemicals in stripping by molecular distillation is reduced.

Transport of butyric acid (BA) through a supported liquid membrane (SLM) containing phosphonium ionic liquid (IL) Cyphos IL-104 and dodecane occurs by two mechanisms. The first is related to the physical solubility of undissociated acid in dodecane in the form of a monomer or dimer and the second to the reactive extraction of acid by IL. Although the model of pertraction indicates that increasing the mean concentration of acid in the feed, c F,lmv, increases the participation of pertraction based on the physical solubility; in the tested range of c F,lmv from 0 kmol m−3 to 0.45 kmol m−3 it does not play an important role and at the highest c F,lmv value, less than 10 % of the overall BA transport were achieved. The presence of IL in SLM considerably increases the value of the overall mass transfer coefficient in pertraction at low BA concentrations. However, at c F,lmv > 0.4 kmol m−3 its values are similar for SLMs with and without IL. Compared to lactic acid, the pertraction of BA through the same SLM is about five times faster. Reactive transport of BA is connected with the back transport of water via reverse micelles decomposition and formation on the extraction and stripping interfaces.

New methods for the determination of carbon in sodium using laser ablation inductively coupled plasma optical emission spectrometry (LA-ICP-OES) and ICP-OES with pneumatic nebulisation (PN-ICP-OES) were developed. The determination was required for the study of the carbon dioxide reaction with molten sodium at high temperatures (300–600°C). After exposition to CO2, the solidified sodium sample was subjected to direct solid analysis by LA-ICP-OES and to solution analysis. For the determination of carbon in the sodium sample surface layer by LA-ICP-OES, three different matrices containing sodium were tested (NaCl, NaF, and Na2B4O7 · 10H2O) as calibration pellets. The calibration dependences were improved using sodium as the internal standard. Average carbon content in the sodium bulk sample was determined by PN-ICP-OES after the sample dissolution by water vapour.

The paper reports a new group of adsorbents obtained by modification of silica surface with silane containing 3-benzylketoimine groups with bonded Cu(II) and Ni(II) chlorides. The adsorbents obtained were subjected to a chromatographic study to establish the type of adsorbate-adsorbent interactions for aliphatic and aromatic halogenated hydrocarbons used as adsorbates. The following retention parameters were determined: retention factor (k), Kovats retention index (I), specific retention volume (V g), and molecular retention index (ΔM e). Values of the molecular retention index were subjected to complex statistical analysis providing qualitative relations between the adsorbates’ properties and spatial structure and their retention. It was observed that bonding of chlorides of Cu(II) and Ni(II) with the ketoimine groups resulted in an increase of the retention index and the molecular retention index indicating an increase of the adsorbate-adsorbent interaction in comparison with the reference column coated with silane including a 3-benzylketoimine group without transition metal chlorides. Along with the observed increase of the adsorbate-adsorbent interaction, larger difference between the retention indices was observed for both halogenated compounds. This indicates a positive influence of the introduced transition metals on the selectivity of the adsorbate-adsorbent interactions of the examined columns.

The paper deals with continuous-time nonlinear adaptive control of a continuous stirred tank reactor (CSTR). Control strategy is based on the application of a controller consisting of a linear and a nonlinear part. The static nonlinear part is derived as an inversion and exponential approximation of measured or simulated input-output data. Design of the dynamic linear part is based on an approximation of nonlinear elements in the control loop by a continuous-time external linear model with directly estimated parameters. In the control design procedure, polynomial approach with the pole assignment method was used. The nonlinear adaptive control was tested by simulations on a nonlinear model of a CSTR with a consecutive exothermic reaction.

Biodiesel-processing factories employing the alkali-catalyzed transesterification process generate a large amount of wastewater containing high amount of methanol, glycerol, and oil. As such, wastewater has high potential to produce biogas using anaerobic treatment. The aim of this research was to investigate the performance of an anaerobic baffled reactor for organic removal and biogas production from biodiesel wastewater. The effect of different organic loading rates, varying from 0.5 kg m−3 d−1 to 3.0 kg m−3 d−1 of chemical oxygen demand, was determined using three 22 L reactors, each comprising five separate compartments. Wastewater was pretreated with chemical coagulants to partially remove oil prior to experimentation. Results show that the anaerobic baffled reactor operated at 1.5 kg m−3 d−1 of chemical oxygen demand and ten days of hydraulic retention time provided the best removal efficiencies of 99 % of chemical oxygen demand, 100 % of methanol, and 100 % of glycerol. Increasing the organic loading rate over 1.5 kg m−3 d−1 of chemical oxygen demand led to excessive accumulation of volatile fatty acids thereby making the pH drop to a value unfavorable for methanogenesis. The biogas production rate was 12 L d−1 and the methane composition accounted for 64–74 %. Phase-separated characteristics revealed that the highest chemical oxygen demand removal percentage was achieved in the first compartment and the removal efficiency gradually decreased longitudinally. A scanning electron microscopic study indicated that the most predominant group of microorganisms residing on the external surface of the granular sludge was Methanosarcina.

A variety of structural analogues of streptolydigin exists in the cultural supernatants of Streptomyces lydicus AS 4.2501. The degradation of streptolydigin in cultural supernatants with different pH values kept at 25°C in a thermostatic bath was investigated using LC-MS/MS detection. Analysis of the alkaline supernatants (pH 9.50) provides evidence of degradation and conversion between streptolydigin and its structural analogues. Interestingly, a new streptolydigin analogue was detected by LC-MS and photo-diode array (PDA) detection in the process of alkaline degradation. After 48 h in a thermostatic bath, the degradation of streptolydigin and its two analogues at pH 9.50 approached pseudo-first order kinetics. Comparatively, the degradation of streptolydigin was much more rapid in the cultural supernatants with pH 3.05, only requiring 2 hours. Qualitative analysis of the degradation products by LC-MS/MS and PDA indicated that hydrolysis of the epoxy ether bond and acid amide bond was the major mechanism of degradation in acidic cultural supernatants. Two degradation products in the acid supernatant were assumed.

A series of five chloride coordination compounds of diethyl (pyridin-4-ylmethyl)phosphate (4-pmOpe) ligand, i.e. [CuCl2(4-pmOpe)2], [NiCl2(4-pmOpe)4], [CoCl2(4-pmOpe)], [ZnCl2(4-pmOpe)2], and [CdCl2(4-pmOpe)2], was prepared and studied. Stoichiometry and stereochemistry of the compounds was confirmed by spectroscopic and magnetic studies as well as by elemental analyses. The 4-pmOpe ligand has a capacity to coordinate to metal ions by means of phosphoryl oxygen and/or nitrogen of pyridine atoms. In Cu(II), Ni(II), and Zn(II) compounds, 4-pmOpe adopts the monodentate coordination mode, bonding metal centers through the pyridine nitrogen atom only. On the contrary, in Co(II) and Cd(II) compounds, 4-pmOpe acts as N,O-bridging ligand forming polynuclear structures. Magnetic studies (1.8–300 K) indicate mononuclear structure of the Co(II) and Ni(II) compounds and suggest existence of a very weak exchange coupling between metal centers in crystal lattice.

The biopolymer (polyhydroxybutyrate) microparticles-calcium phosphate composites were prepared by mechanical mixing of the basic composite components with the addition of hardening liquid after ethanol-composite mixture suspension moulding. The composite microstructures were more compact than the pure cement samples as confirmed by the lower values of specific areas and mesopore volumes. Both the specific areas and mesopore volumes decreased with soaking time in a simulated body fluid. The low polyhydroxybutyrate degradation in composites was found after soaking in simulated body fluid, which was terminated after one week. The formation of a dense apatite layer bonded directly to the surface of polyhydroxybutyrate microparticles was observed. The highest diametral tensile strength (13 MPa) and compressive strength (95 MPa) values of up to 50 % higher than in pure cement were measured in samples with 10 % of polyhydroxybutyrate. The addition of polyhydroxybutyrate microparticles had no effect on the setting time.

Intercalation of basic amino acids into layered zirconium proline-N-methylphosphonate phosphate (α-ZPMP) was investigated at room temperature. Three kinds of host-guest compounds were prepared and characterised by elemental analysis, inductively coupled plasma analysis (ICP), Fourier transform infrared spectrum (FT-IR), Raman spectrum, X-ray powder diffraction (XRD) and thermoanalysis. The interaction of amino acid guests with P-OH of α-ZPMP host was documented by FT-IR and Raman spectra. In addition, the XRD patterns indicated that l-arginine or l-lysine were intercalated into the interlayer galleries of α-ZPMP host; the interlayer distances of the Larginine and l-lysine intercalation compounds were expanded from 1.520 nm to 2.218 nm and 2.207 nm, respectively. l-arginine and l-lysine would be arranged as a mono-molecule layer in different orientations. The interlayer distance of l-histidine (d = 1.522 nm) was similar to that of α-ZPMP host (d = 1.520 nm), l-histidine might be adsorbed on the outer surface of the α-ZPMP host. Thermoanalysis showed that the intercalated l-arginine and l-lysine were removed at 110–305°C or 150–250°C, respectively, the adsorbed l-histidine was released at a temperature of up to 320°C.

Double-scale composite lead zirconate titanate Pb(Zr0.52Ti0.48)O3 (PZT) thin films of 360 nm thickness were prepared by a modified composite sol-gel method. PZT films were deposited from both the pure sol and the composite suspension on Pt/Al2O3 substrates by the spin-coating method and were sintered at 650°C. The composite suspension formed after ultrasonic mixing of the PZT nanopowder and PZT sol at the powder/sol mass concentration 0.5 g mL−1. PZT nanopowder (≈ 40–70 nm) was prepared using the conventional sol-gel method and calcination at 500°C. Pure PZT sol was prepared by a modified sol-gel method using a propan-1-ol/propane-1,2-diol mixture as a stabilizing solution. X-ray diffraction (XRD) analysis indicated that the thin films possess a single perovskite phase after their sintering at 650°C. The results of scanning electron microscope (SEM), energy-dispersive X-ray (EDX), atomic force microscopy (AFM), and transmission electron microscopy (TEM) analyses confirmed that the roughness of double-scale composite PZT films (≈ 17 nm) was significantly lower than that of PZT films prepared from pure sol (≈ 40 nm). The composite film consisted of nanosized PZT powder uniformly dispersed in the PZT matrix. In the surface micrograph of the film derived from sol, large round perovskite particles (≈ 100 nm) composed of small spherical individual nanoparticles (≈ 60 nm) were observed. The composite PZT film had a higher crystallinity degree and smoother surface morphology with necklace clusters of nanopowder particles in the sol-gel matrix compared to the pure PZT film. Microstructure of the composite PZT film can be characterized by a bimodal particle size distribution containing spherical perovskite particles from added PZT nanopowder and round perovskite particles from the sol-matrix, (≈ 30–50 nm and ≈ 100–120 nm), respectively. Effect of the PZT film preparation method on the morphology of pure and composite PZT thin films deposited on Pt/Al2O3 substrates was evaluated.

New 2-substituted diazaphospholane-2-oxides (I-III, V-VIII) and diazaphosphorinane-2-oxide (IV) were synthesised and characterised by 1H, 13C, and 31P NMR, IR spectroscopy, and elemental analysis. The presence of chiral diamino groups in compounds II and V–VIII gives rise to various diastereomers so that the 31P{1H} NMR spectra demonstrated three and two peaks with different ratios, respectively. Also, the 1H and 13C{1H} NMR spectra of compounds II and V–VIII revealed three and two sets of signals for the related conformers (diastereomers). Interestingly, the 31P NMR spectrum of V in D2O indicated a great upfield shift (Δδ = 19.0) for 31P relative to the value obtained in DMSO-d6 (solvent effect). The two signals in V split further to three signals in the presence of β-cyclodextrin. Moreover, conformational analysis of diazaphospholane V was studied by ab initio calculations at the HF and B3LYP levels of theory using the Gaussian 98 program. Results indicated that among four suggested diastereomers (C1–C4) of V, C1 and C3 containing methyl group in the equatorial position are the most stable forms.

A series of new 3-(2-morpholinoquinolin-3-yl)acrylonitrile derivatives (IVa-IVf) has been synthesised by the base-catalysed condensation reaction of 2-morpholinoqionoline-3-carboxaldehydes (IIa-IIc) and 2-cyanomethylbenzimidazoles (IIIa-IIIb). Subsequent regiospecific reduction of the C—C double bond in acrylonitrile moiety afforded 3-(2-morpholinoquinolin-3-yl)propanenitrile derivatives (Va-Vf). All the compounds synthesised were subjected to in vitro antimicrobial screening against some representatives of bacteria and fungi. The majority of the compounds were found to be active against Gram-positive bacteria Bacillus subtilis and Clostridium tetani as well as against the fungal pathogen Candida albicans.

Silicon-based thiourea (SiliaBond® Thiourea) (Si-THU), a heterogeneous catalyst, has been applied to the highly selective C-S bond formation via Michael addition of thiols to α,β-unsaturated carbonyl compounds under solvent-free conditions at 55–60°C. The thio-Michael addition products were obtained in an excellent yield under optimised conditions. This methodology involving a metal-free as well as a metal scavenger catalyst has been found to be an alternative method for the thio-Michael addition reaction.

A convenient method for the synthesis of tetrahydrobenzo[b]pyrans by a one-pot three-component cyclocondensation of dimedone, aryl aldehydes, and malononitrile in water using silica gel-supported polyphosphoric acid (PPA-SiO2) as an efficient and reusable catalyst is described. The present methodology offers several advantages, such as a simple procedure with ease of handling, short reaction time, high yields, and the absence of any volatile and hazardous organic solvents.

In this study, biodiesel has been successfully produced by transesterification using non-catalytic supercritical methanol and methyl acetate. The variables studied, such as reaction time, reaction temperature and molar ratio of methanol or methyl acetate to oil, were optimised to obtain the optimum yield of fatty acid methyl ester (FAME). Subsequently, the results for both reactions were analysed and compared via Response Surface Methodology (RSM) analysis. The mathematical models for both reactions were found to be adequate to predict the optimum yield of biodiesel. The results from the optimisation studies showed that a yield of 89.4 % was achieved for the reaction with supercritical methanol within the reaction time of 27 min, reaction temperature of 358°C, and methanol-to-oil molar ratio of 44. For the reaction in the presence of supercritical methyl acetate, the optimum conditions were found to be: reaction time of 32 min, reaction temperature of 400°C, and methyl acetate-to-oil molar ratio of 50 to achieve 71.9 % biodiesel yield. The differences in the behaviour of methanol and methyl acetate in the transesterification reaction are largely due to the difference in reactivity and mutual solubility of Jatropha curcas oil and methanol/methyl acetate.

The paper evaluates the possibilities and limitations in characterising photochemical properties of individual kinetically labile species being in mutual equilibrium. A model of calculating quantum yield values is elaborated and applied to azidokojic iron(III) complexes in aqueous solutions. Based on the known speciation of the complexes as a function of pH, Fe(III) and azidokojic acid concentrations, electronic absorption spectra of individual species, and the determined overall quantum yield of Fe(II) photoformation at irradiation with monochromatised radiation at 366 nm, the quantum yield of Fe(III) to Fe(II) photoreduction was obtained for each of the complexes present in the investigated systems.

Petroleum ether-benzene extract of the leaves of Ficus krishnae afforded a novel halogenated 2H-chromen-2-one named 3-chloro-7-methoxy-4-methyl-chromen-2-one. Its structure was established on basis of chemical and physical evidence (IR, 1H NMR, and MS data) as well as on X-ray crystallographic studies.

A new and efficient method for the synthesis of novel 4β-isocyanopodophyllotoxins as a valuable building block for the synthesis of versatile bioactive podophyllotoxin analogues under both classical and ultrasonic conditions was developed. In general, significant improvements in rates of reaction and yields of sonochemical reactions relative to the classical ones were observed.

An efficient and environmentally benign one-pot method for the synthesis of 1-methyl-2,6-diarylpiperidin-4-ones using montmorillonite K-10 as a catalyst has been developed. Antimicrobial activity of the compounds has been tested against selected representatives of Gram-positive and Gram-negative bacteria and fungi.