Band 65, Heft 6

A rapid and simple ionic liquid-based dispersive liquid-liquid micro-extraction (DLLME) method has been developed to pre-concentrate four paraben preservatives (methylparaben, ethylparaben, propylparaben, and butylparaben) from street food (pancakes). Several potentially influential factors such as the type of ionic liquid and disperser solvent, extraction time, sample pH, ionic strength, and the volume of the ionic liquid and disperser solvent were investigated. The optimum experimental conditions for the proposed micro-extraction process were: 0.1 mL of 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM][PF6]) as an extraction solvent, 0.1 mL of acetonitrile as a disperser solvent, 5 min extraction time, and sample ionic strength of 30 % sodium chloride in water sample at pH 6.0. The LODs and LOQs were in the range of 1.0–1.5 ng g−1 and 3.5–4.5 ng g−1, respectively. Spiking recoveries were in the range of 60.1–79.5 % and the associated RSDs were all in the range of 1.8–7.0 %. The results show that DLLME is a suitable method for the determination of parabens in pancake samples and ionic liquid is a good extractant in this process.

Simultaneous determination of enalapril maleate (ENA) and nitrendipine (NIT) in pharmaceutical preparations was performed using liquid chromatography (LC) and the partial least-squares-1 (PLS-1) method. In LC, the separation was achieved on a C8 column and the optimum mobile phase for good separation in a gradient elution programme was found to be acetonitrile-water (φ r = 81: 19) and optimum flow-rate, temperature, injection volume, and detection wavelength were set at 1.0 mL min−1, 25°C, 10 μL, and 210 nm, respectively. Dienogest was selected as an internal standard. In the spectrophotometry, a PLS-1 chemometric method was used. The absorbance data matrix related to the concentration data matrix was established by measurement of absorbances in their zero order spectra with an increment of Δλ = 1 nm in the 220–290 nm range for ENA and with Δλ = 1 nm in the 230–290 nm range for NIT in the PLS-1 method. Following this step, calibration was established by using this data matrix to predict the unknown concentrations of ENA and NIT in their binary mixture. These optimised methods were validated and successfully applied to a pharmaceutical preparation in tablet form and the results were subjected to comparison.

The chemiluminescence behaviour and mechanism of peroxynitrous acid and Ru(bpy)32+ were studied in the presence of short-chain alcohols (methanol, ethanol, propan-1-ol, propan-2-ol, butanol, 2-methylpropan-1-ol, pentanol). It was found that the chemiluminescence intensity of peroxynitrous acid and Ru(bpy)32+ system could be significantly enhanced by these seven short-chain alcohols. The maximum chemiluminescence wavelength of 608 nm of [Ru(bpy)32+]* in the excited state was attributed to the reaction between Ru(bpy)32+ and dihydroxyalkyl radicals which were generated during the redox course of peroxynitrous acid and alcohols. In addition, the chemiluminescence signals of the system presented depended largely on the solubility and branched-chain structure as well as the length of carbon chain. The analytical characteristics and parameters of the peroxynitrous acid/Ru(bpy)32+/alcohols chemiluminescence system were investigated under optimum conditions.

The applicability of laser ablation (LA) inductively coupled plasma (ICP) spectrometry for assessing elemental distributions in layered ceramics was investigated and compared with electron probe microanalysis (EPMA). Ordinary glazed wall tiles were employed as model specimens due to their defined structure and composition. They were used for calibration in the analysis of ancient pottery. A qualitative depth profile was acquired by single-spot laser drilling perpendicular to coatings with a Nd:YAG (1064 nm) laser coupled with an ICP optical emission spectrometer (OES). The lower lateral resolution associated with the laser spot diameter of 1.0 mm led to smoothing of the depth profile due to the averaging of local irregularities. In addition, transverse line scans by ablation across the tile section using an ArF* (193 nm) laser coupled with an ICP mass spectrometer (MS) were performed. LA-ICP-OES depth profiles and LA-ICP-MS transverse scans were validated by EPMA section scans and 2D back-scattered electrons images. The LA-ICP-OES acquisition was less dependent on sample surface and layer irregularities, whereas the transverse line scan over the tile section with the small-spot beam offered insight into the micromorphology of the individual layer. The combined approach revealed the occurrence of individual mineral grains, micro-heterogeneities and the character of interfaces between layers.

A rapid kinetic method for the simultaneous determination of levodopa, dopamine, and dobutamine was examined and developed. It was based on a consecutive reaction of a reduction of Cu(II) to Cu(I) by catecholamines, followed by the complexation of Cu(I) with neocuproine to form a yellow product in an acetic acid-acetate buffer. Spectrophotometric data were recorded at 453 nm (wavelength at the yellow complex absorption maximum) for 300 s. Linear calibrations were obtained in the concentration ranges of (0.08–1.44) × 10−5 mol L−1, (0.08–1.44) × 10−5 mol L−1, and (0.16–1.44) × 10−5 mol L−1 for levodopa, dopamine, and dobutamine, respectively. A variety of multivariate calibration models was developed for simultaneous analysis of the three analytes; while most models produced satisfactory prediction results for synthetic samples, the hybrid linear analysis method was arguably the best-performing (relative prediction error, RPET = 6.6 %). The proposed method was applied to an analysis of spiked rabbit serum samples and the results showed good agreement with the high performance liquid chromatography measurements.

Ionic liquid (IL) 1-ethyl-3-methylimidazolium dimethylphosphate ([Emim]DMP) was chosen as an environment-friendly solvent to enzymatically hydrolyze cellulose in situ. Under optimal reaction condition, 80.2 % of cellulose (10 mg mL−1) were converted to glucose in aqueous-IL-DMSO (φ r = 74: 25: 1) media at 55°C in 18 h. Finally, fermentability of the recovered hydrolyzates was evaluated using Saccharomyces cerevisiae which is able to ferment hydrolyzates efficiently, the ethanol production was 0.44 g g−1 of glucose within 24 h of the process. Such information is vital for the saccharification of more complex cellulose materials and for the fermentation of hydrolyzates into biofuel.

A three-level central composite design of the Response Surface Methodology and the Artificial Neural Network-linked Genetic Algorithm were applied to find the optimum operating conditions for enhanced production of l-asparaginase by the submerged fermentation of Aspergillus terreus MTCC 1782. The various effects of the operating conditions, including temperature, pH, inoculum concentration, agitation rate, and fermentation time on the experimental production of l-asparaginase, were fitted to a second-order polynomial model and non-linear models using Response Surface Methodology and the Artificial Neural Network, respectively. The Artificial Neural Network model fitted well, achieving a higher coefficient of determination (R 2 = 0.999) than the second-order polynomial model (R 2 = 0.962). The l-asparaginase activity (38.57 IU s mL−1) predicted under the optimum conditions of 32.08°C, pH of 5.85, inoculum concentration of 1 vol. %, agitation rate of 123.5 min−1, and fermentation time of 55.1 h was obtained using the Artificial Neural Networklinked Genetic Algorithm in very close agreement with the activity of 37.84 IU mL−1 achieved in confirmation experiments.

Tall oil soap as a waste product of the sulphate cellulose production process was treated by single-stage liquid-liquid extraction. The aim of this study was to compare yields of health beneficial matters contained in tall oil soap when several extraction solvents, recommended in literature, were used. Hexane, 1-methyl-4-(1-methylethenyl)-cyclohexene, 2-methylpropan-1-ol, hexan-1-ol, 4-methylpentan-2-one, 2-methoxy-2-methylpropane, and butyl ethanoate were tested. For hydrocarbons it was necessary to add a de-emulsifier into the system, which limits the formation of foams and stable emulsions. The highest yields of total phytosterols (78 %) and especially of β-sitosterol (100 %) were reached when butyl ethanoate was used. However, it was necessary to adjust pH of the treated raw material to approximately 7. The highest yields for feed where pH was not adjusted were obtained with 2-methylpropan-1-ol: 67 % of total sterols and 89 % of β-sitosterol. Disadvantages of most of the tested solvents included the formation of the undesirable solid interphase which could not be removed, partial solubility of the solvents in the water phase, their high boiling point and/or instability. These disadvantages prevent the use of these solvents in industrial applications; they also complicate the treatment of tall oil soap by liquid-liquid extraction or the regeneration of the used organic solvent.

Activated Sludge Model No. 1 (ASM1) was used to model the biological stage of an actual waste water treatment plant (WWTP). Some possibilities for the utilisation of simulation programs for WWTP operation are presented. Simulation calculations were performed taking the conditions of WWTP in Nové Zámky, the Slovak Republic, into consideration, where measurements of the diurnal variations in waste water flow and composition at the inlet and outlet were carried out. A calibrated model predicting the influence of changes in the waste water composition and the operational parameters on the effluent waste water quality and related operational costs is available. Values of the operational parameters (solids retention time, internal recirculation flow, dissolved oxygen concentration) for effective operation (effluent concentration values, oxygen consumption, charges, i.e. charges for waste water discharge into the recipient water body) of the WWTP were obtained by simulations. The presented results are for illustration purposes only and are not intended as instructions for the operation of a waste water treatment plant. They correspond to the calibrated mathematical model ASM 1 based on the results of experimental measurements and operational data, as well as on the technical and monitoring level of the WWTP.

Hornification is the loss of fiber wall swelling which is detrimental to subsequent recycling resulting from drying. It is known that dried fibers lose their conformability and swelling capacity. The effect of recycling treatment on the swelling ability of hardwood bleached kraft pulp fibers was determined. Modelling paper recycling, sheets were recycled using heat treatment (23°C, 60°C, 100°C). The results were compared with those for natural fibers from bleached kraft pulp. Swelling kinetics of sheets was measured by a modified method monitoring interactions of pulp with water. Swelling ability decreased during the recycling in comparison with never-recycled pulp at all temperatures. Recycling of sheets caused only small changes in the cupri-ethylene-diamine viscosity, however, the water retention value decreased considerably.

Zirconium(IV) 4-sulphophenylethyliminobismethylphosphonate (ZSBEDP) was prepared and characterised by elemental analysis, IR, TG-DSC, and XRD. ZSBEDP was found to be an efficient catalyst for the Biginelli reaction of aromatic aldehyde, ethyl acetoacetate, and urea or thiourea under solvent-free conditions so as to give 3,4-dihydropyrimidones in good to excellent yields. The catalyst can be separated by simple filtration and reused without significant loss of its catalytic activity.

Monitoring the enforcement of an EU-wide ban of nitrofuran antibiotics in the food production chain is a challenging task, given the nature of nitrofuran compounds. The original and modified Fenton reactions are advanced oxidation processes that can eliminate the toxicity of nitrofurans. 2-(5-Nitrofuryl)acrylic acid (I) was degraded as a model compound by the original Fenton reaction with ferrous sulphate, by Mohr’s salt at pH 3 and 7, and finally by advanced Fenton process (AFP) (Fe0/H2O2/H2SO4). In addition, the growth inhibition of Escherichia coli, a G− bacterium, was tested both before and after AFP treatment. The results showed that a small degradation efficiency of this treatment process led to the toxicity changes and that the toxicity of I after AFP treatment process decreased. It seems that the treatment of polluted water using the Fenton reaction and its modifications would be a suitable method for degradation of nitrofuran derivatives in polluted water.

Double hydroxides containing alkaline earth and iron(III) ions were synthesised by the co-precipitation method. The solid materials obtained were characterised by a range of instrumental methods (powder X-ray diffractometry, thermogravimetry, scanning electron microscopy, energy dispersive X-ray fluorescence spectrometry, elemental maps, and infrared spectroscopy). It was found that the Ca(II)Fe(III), Mg(II)Fe(III), and Ba(II)Fe(III) double hydroxides had layered structures, while Sr(II)Fe(III) had not. The optimum conditions for synthesis of Ca(II)Fe(III)-layered double hydroxides (materials to be used in further studies) were also elaborated.

A pH-induced conformational transition of atactic poly(2-methylprop-2-enoic acid) (poly(methacrylic acid), PMMA) from the contracted to expanded conformation was investigated by viscometry, potentiometric titration, and anthracene solubilisation in the presence of low-molecular-mass non-ionogenic co-solutes-glucose, α-cyclodextrin (αCD), and γ-cyclodextrin (γCD), respectively. No effect of glucose and αCD on the conformational transition was observed with either of the methods used. On the other hand, the characteristic features of the conformational transition were absent in the presence of γCD. The different effects of the co-solutes indicate that the interaction between PMAA and γCD corresponds to the partial inclusion of the PMAA chain into the γCD cavity. The viscometry and anthracene solubilisation imply that γCD promotes the expanded conformation of PMAA at low pH. The potentiometric titration does not support this conclusion. Even though there is no break on the Henderson-Hasselbalch plot, a characteristic of the conformational transition, the potentiometric behaviour corresponds to that of the contracted PMMA conformation. Thus the results suggest the hierarchical picture of the PMAA conformation at low pH in which the local arrangement of the PMAA chain is a prerequisite for clustering on a larger scale.

Glycidoxypropyltriethoxysilane (GPS) was used as a reactive silane to graft metal- complexing ligands onto silica gel in aqueous media under mild conditions. The synthesis entailed the reaction of GPS with silica gel, followed by grafting polyamine onto the epoxy functional group. GPS was added to silica gel in ethanol with 5 vol. % water and the mixture was air-dried for 24 h. Subsequently, excess amounts of polyamines: triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine were individually added to the silanised silica, followed by solvent evaporation and ovendrying at 60°C. The ligand-grafted silica gel particles showed a rapid heavy metal uptake in batch or flow-through experiments with capacities reaching 0.1 mmol g−1 for copper, zinc, cadmium, or lead ions. Columns packed with the modified particles could be readily regenerated by acid-washing with only a small decrease in activity. The particles could be used for the colourimetric detection of heavy metal pollution or for pre-concentration for analytical purposes. Competition between Cu2+, Zn2+, Pb2+, and Cd2+ ions for the three synthesised silica showed that Cu2+ ions were adsorbed more strongly than the other metal ions. The general method developed can be applied to graft other molecules with terminal amino groups for other purposes.

A series of neutral gelators and cationic amphiphiles derived from 1,2 diphenylethylenediamine (I) and 1,2-cyclohexanediamine (II) was synthesised. Helical silica nanotubes were prepared utilising these organic gelators through sol-gel polycondensation of tetraethoxy silane, (TEOS-silica source). Right- and left-handed helical nanotubes respectively were obtained from a 1: 1 mass mixture of optically active, (1S,2S)-III-(1S,2S)-V neutral gelator and (1S,2S)-IV-(1S,2S)-VI cationic amphiphile and a 1: 1 mass mixture of optically active, (1R,2R)-III-(1R,2R)-V neutral gelator and (1R,2R)-IV-(1R,2R)-VI cationic amphiphile, indicating that the handedness of the helical nanotubes varied with the change in the neutral gelator precursors used. The nanotubes were characterised by SEM images.

Zinc was bound on montmorillonite K10 by cation exchange to obtain a catalyst named clayzic. In the Friedel-Crafts benzylation of 1,4-dimethoxybenzene, this catalyst was used for the synthesis of substituted diphenylmethanes using 4-chlorobenzyl chloride and 4-bromobenzyl bromide. During the reaction, sub-products from a second benzylation reaction process were observed. For a better understanding of their formation, reactions were carried out at different times to obtain data on the progress of benzylation and the relative ratio of each product was calculated using two different analytical methods. It was shown that the selectivity and reactivity of both aryl halides were reversed under these experimental conditions contrary to those obtained using the more conventional catalyst, zinc dichloride. These results were explained by geometrical and electronic considerations. It was found that the formation of transition states and Wheland intermediates from aryl bromide and chloride in the presence of clayzic can be explained in terms of preferential absorption. Moreover, the high percentage of 4-chlorobenzyl chloride conversion was attributed to its covalent radius, which is smaller than that of Br. At the same time it was shown that the presence of a Brönsted acid, due to the liberation of HCl during the benzylation, is responsible for the poisoning of the clayzic catalyst. Moreover, poisoning effect of the bromine anion could not be excluded.

A new series of 1,2,3-selenadiazoles containing an aryl or a 3-arylisoquinoline sulfanyl moiety at carbons 4 and 5, respectively, was prepared by cyclization of the respective semicarbazones in the presence of selenium(II) oxide and tetrahydrofuran at 70–75°C. Semicarbazones required for the reaction were obtained from 2-((3-arylisoquinolin-1-yl)sulfanyl)-1-phenylethanones, I, by a reaction with semicarbazide hydrochloride in ethanol/water mixture and potassium acetate base.

Three series of heteroaryl chalcones, (E)-1-(2-pyridyl)-3-(X)prop-2-en-1-one (Ia-Ic), (E)-1-(2-thienyl)-3-(X)prop-2-en-1-one (IIa-IIc), and (E)-1-(2-furyl)-3-(X)prop-2-en-1-one (IIIa-IIIc), where X = 2,4,5-trimethoxyphenyl (for series a), X = 2,4,6-trimethoxyphenyl (for series b), and X = 3,4,5-trimethoxyphenyl (for series c) were synthesised using basic catalysed aldol condensation and characterised using 1H NMR and FT-IR spectroscopies. Compound IIa was also characterised by single crystal X-ray analysis. The absorption and fluorescence emission spectra of these compounds revealed that the absorption and fluorescence depended on the heterocycle rings and trimethoxysubstituted phenyl rings linked to the enone system. The position of methoxy groups substantially affected the fluorescent properties. Compounds Ia-IIIa containing the 2,4,5-trimethoxyphenyl moiety exhibited the red-shift phenomenon and strong emission fluorescence.

A simple, inexpensive and efficient one-pot synthesis of 1,4-dihydropyridine derivatives under solvent-free conditions using silica sulphuric acid (SSA) as a heterogeneous and recyclable catalyst is reported.

A number of studies and works in drug delivery literature are focused on the understanding and modelling of transport phenomena, the pivotal point of a good scaffold design for tissue engineering. Accurate knowledge of the diffusion coefficient of an active drug plays a key role in the analysis, prediction of their kinetics and formulation of efficient drug delivery systems. In this work, the kinetics of the release of methylprednisolone from agar-Carbomer hydrogel were studied taking into consideration the different drug concentrations and clearances typically achieved in in vitro or in vivo tests. Starting from the experiments it is possible to model the transport phenomenon and to calculate the diffusion coefficient through the hydrogel matrix.

The inhibition of the oxygen evolution rate (OER) in Chlorella vulgaris by 2-alkylsulphanyl-4-pyridinecarbothioamides (APCTs; alkyl = methyl up to hexadecyl) was studied. APCTs were found to inhibit photosynthetic electron transport (PET) which resulted in the inhibition of OER in algae. The inhibitory activity of APCTs was highly dependent on the alkyl chain length of the 2-alkylsulphanyl substituent and the corresponding dependence showed a bilinear course with the decyl derivative as being the most active inhibitor. Using EPR spectroscopy, the site of APCT action in the algal photosynthetic apparatus was determined. It was confirmed that APCT interacted mainly with the D. intermediate, i.e. with tyrosine radical (TyrD) occurring at the 161st position in D2 protein which is situated on the donor side of photosystem 2.