Band 70, Heft 6

Matrix effects and practical possibilities of reducing accompanying non-spectral interferences in inductively coupled plasma optical emission spectrometry (ICP-OES) were studied for microconcentric Micromist, concentric and V-groove nebulizers (VGN) coupled with two cyclonic spray chambers of different sizes. The effect of a wide scale of interferents and mixtures thereof in the concentration range of up to 2 mass % (Na, Ca, Ba, La, urea) or up to 20 vol. % (nitric acid) on the analysis of Cd, Cu, K, Mg, Mn, Pb and Zn was investigated in terms of their analytical recovery and Mg(II) 280.27 nm/Mg(I) 285.29 nm line intensity ratio. Recoveries of ionic lines were lower than those of atomic lines (37–102 %) depending on the matrix concentration. The Mg(II)/Mg(I) ratios were found to be 12–15 and they slightly decreased as the matrix load increased. Exceptional behavior of pure La matrix, steeply lowering the recoveries and Mg(II)/Mg(I) ratios was observed. A Micromist nebulizer coupled with a small inner volume spray chamber provided the highest recoveries (94–102 %), lowest matrix effects across the matrix loads and, compared to others, the least significant dependence without worsening of the analytical characteristics (recoveries, signal background ratios and the Mg(II)/Mg(I) ratios) across the studied matrices.

Two newly synthesised 1,8-naphthalimide-based proton-receptor fluorescent probes N -allyl-4-(4′- N , N -diethylpropionamide-acetamido-piperazinyl)-1,8-naphthalimide I and N -( N , N -dibenzylpro-pionamide-acetamido)-4-allyl-1-piperazinyl-1,8-naphthalimide II were synthesised to monitor the change in pH in such a way that the presence of protons can increase the fluorescence intensity of these compounds. Unlike most of the other pH-sensitive probes reported, the probes possess the obvious advantage of being able to detect stronger acids at pH ≈ 2 and a combination of the two probes could detect a wider pH scale from 1.98 to 6.59; this should be very useful for monitoring the pH of the environment.

This study reports the fabrication of an amperometric cholesterol biosensor based on cholesterol oxidase (ChOx), SnO 2 NPs and Nafion-modified carbon paste enzyme electrodes (CPE/SnO 2 NPs-ChOx/Naf). The electrochemical characterisations of BCPE and CPE/SnO 2 NPs were performed using CV and EIS. The determination of cholesterol was carried out by electrochemical oxidation of H 2 O 2 at 0.6 V vs. Ag/AgCl. The CPE/SnO 2 NPs-ChOx/Naf presented a linear range from 0.20 μmol L −1 to 4.95 μmol L −1 with a low limit of detection (0.04 μmol L −1 ). In addition, the optimal values for pH and temperature were found to be 7.5 and 35°C, respectively. The CPE/SnO 2 NPs-ChOx/Naf was used for the determination of cholesterol in serum samples and good results were obtained

Received 1 August 2015; Revised 23 November 2015; Accepted 26 November 2015 The most acceptable method for preparing glycerophosphocholine is to hydrolyse the natural phosphatidylcholine and use the quaternary ammonium base resin, as a promising heterogeneous catalyst can simplify the craft and minimise the problems existing in the homogeneous catalytic process. However, most of the resins reported in the literature are commercial trimethyl benzyl ammonium base resins and the application of other longer carbon-chain quaternary ammonium resins has not been reported. In the present work, a series of quaternary ammonium base resins were prepared from chloromethyl polystyrene microspheres and different tertiary amines and were used to prepare glycerophosphocholine from natural phosphatidylcholine. The factors affecting the exchange capacity and activity of the resin were investigated. The results showed that the resin possessed a better activity and stability under the following conditions: 1,4-dioxane as solvent, triethylamine as amination agent, reaction temperature of 60°C and amination time of 3 h; it was then used in the methanolysis of phosphatidylcholine by ultrasound-assisted reaction at ambient temperature, with the conversion of phosphatidylcholine attaining 97 % after 4 h. The catalyst was easy to separate from the reaction mixture and could also be readily available for repeat use; the activity and stability were largely consistent after six repeat uses.

Phyllanthus amarus is known as a healing herb which has traditionally been used in the treatment of various diseases such as hepatitis, diabetes and cancer. The extraction parameters have great effects on the extraction efficiency of bioactive compounds and pharmacological activity of the extracts. This study sought to optimise the microwave-assisted extraction parameters for phenolic compounds-enriched extracts and antioxidant capacity from P. amarus using response surface methodology (RSM). The results showed that the optimal microwave-assisted extraction parameters were an extraction time of 30 min, an irradiation time of 14 s min −1 and a ratio of solvent to sample of 150 mL g −1 . The total phenolic content, phenolic extraction efficiency, saponin content, 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) radical scavenging capacity, 2,2-diphenyl-1-picryl-hydrazil (DPPH) radical scavenging capacity and ferric reducing antioxidant power of the P. amarus achieved under these optimal parameters were 87.3 mg of gallic acid equivalents (GAE) per gram of dried sample, 69.7 % , 134.9 mg of escin equivalents (EE) per gram of dried sample, 997.8, 604.7 and 437.3 all in mg of trolox equivalents (TE) per gram of dried sample, respectively, which were not significantly different from the predicted values (86.9 mg of GAE per gram of dried sample, 67.3 % , 123.5 mg of EE per gram of dried sample, 1013.3 mg of TE per gram of dried sample, 530.6 mg of TE per gram of dried sample and 423.5 mg of TE per gram of dried sample, respectively). Accordingly, the optimal microwave-assisted extraction parameters of 30 min, 14 s min −1 and 150 mL g −1 are recommended for the extraction of enriched phenolics from P. amarus for potential application in the nutraceutical and pharmaceutical industries.

Headspace solid-phase micro-extraction (HS-SPME) and ultrasonic solvent extraction (USE) were used for red clover honey volatiles extraction. The extracts were analysed using gas chromatography and mass spectrometry (GC-MS). Lilac aldehyde isomers dominated in the headspace (individual range from 7.6 % to 21.4 %) followed by phenylacetaldehyde (10.1-31.2 %) and benzaldehyde (7.0-15.7 %). Higher aliphatic alcohols and hydrocarbons were the predominant constituents of the honey extracts. The honey and its extracts exhibited rather weak anti-radical activity (DPPH assay) and total antioxidant activity (FRAP assay). On the other hand, the honey’s inhibitive properties towards the corrosion of AA 2017A alloy in NaCl solution (potentiodynamic polarisation and potentiostatic pulse measurements) revealed the honey to be a very good anodic inhibitor (efficiency up to 76 %) while the honey extracts (USE) showed better inhibition efficacy.

Vacuum membrane distillation was used to concentrate organic solutions containing mainly 1,3-propanediol, ethanol and carboxylic acids. The studied solutions were permeates obtained from nanofiltration process applied for the separation of broths from the fermentation of glycerol with the Citrobacter freundii bacteria. The presence of organic solutes decreased the surface tension of permeates to the value of 47 mN m −1 . However, the pores inside the used polypropylene membranes were not wetted by the post-fermentation solutions, and they were concentrated to over five-fold. It was shown that vacuum membrane distillation has over twice higher thermal efficiency compared to that obtained by direct contact membrane distillation.

This study reports the research results on a mixing process using a stirred tank mixer under the action of a rotating magnetic field (RMF). Dimensionless correlations are proposed to predict the power consumption and mixing time for the mixing systems analysed. The results suggest that the mixing behaviour of the experimental set-ups tested may be assessed using the dimensionless mixing energy as the product of the power input and mixing time. In addition, an innovative strategy is proposed on the basis of the synergistic effect of the rotational Rushton turbine and the RMF generator. The values of the dimensionless energy thus obtained were used to compare the mixing process performed by the mixing devices tested. It is shown that the mixing process under the RMF action has significantly higher values of energy consumption than the conventional Rushton turbine. The total energy consumption for the mixing process performed by the RMF mixer may be reduced by concomitant use of a rotational agitator.

A new Au(III)-imprinted hydrogel (Au(III)-Imp) was prepared by the photopolymerisation of 4- acryloylmorpholine (AcM), 2-hydroxyethyl acrylate (HEA), and poly(ethylene glycol) diacrylate (cross-linking monomer, PEG-DA) in the presence of gold ions. In addition, non-imprinted hydrogel (N-Imp) was similarly prepared without Au(III) ions The Au(III)-Imp hydrogel was characterised by several techniques. To achieve the optimal conditions, effect of pH, time, and initial metal ion concentrations were investigated using a batch system. The pre-concentration factor for Au(III) ions was found to be at least 100. The analytical parameters of the method were determined and the method was also successfully applied to computer circuit board scrap samples. The reusability of the Au(III)-Imp hydrogel was also determined.

A presulphided treatment was applied to the oxidic Ni-Mo-Zn/Al 2 O 3 catalyst (nickel catalyst) in order to avoid thermal run-away during initiation of the hydrogenation of pyrolysis gasoline. The physico-chemical properties of the prepared oxidic nickel catalyst, the reduced and passivated (RP) nickel catalyst and the sulphided (RPS) nickel catalyst were characterised using N 2 adsorptiondesorption, X-ray diffraction, temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS). The TPR results showed that the reducibility of the RP Ni-Mo-Zn/Al 2 O 3 catalyst was improved over the oxidic nickel catalyst. The XPS spectra confirmed the binding energy of the RPS nickel catalyst to be higher than that of the oxidic nickel catalyst. The catalytic performance was evaluated on a fixed-bed reactor (reaction temperature between 30 °C and 70°C, at 2.8 MPa of total pressure and weight hourly space velocity of 2.0 h -1 , the volume of H 2 /pyrogasoline = 200 : 1). The rising temperature of the RPS nickel catalyst was almost 20 °C lower than that of the oxidic nickel catalyst during the initial stage of the hydrogenation reaction. The results indicated that the RPS nickel catalyst exhibited better stability than the oxidic nickel catalyst during the start-up period, thereby providing a better selectivity in long- term operation.

Water disinfection making use of an ultraviolet (UV) reactor is an attractive procedure because it does not produce any by-products. In this work, the effects of pipe roughness on the performance of a closed-conduit water disinfection UV reactor were investigated. In order to incorporate the surface roughness effects, a simple, stable, highly accurate model, better than any iterative approximation, was adopted in the numerical simulations. The analysis was carried out on the basis of two performance indicators: reduction equivalent dose (RED) and system dose distribution. The analysis was performed using a commercial computational fluid dynamics (CFD) tool (ANSYS Fluent). The fluence rate within the UV reactor was calculated using UVCalc3D. The pipe surface roughness resulted in longer pathogen residence times and higher dose distribution among the pathogens. The effect of pipe surface roughness on RED depends on the Reynolds number and relative roughness. Pipe surface roughness plays an important role because UV reactors for water disinfection operate at moderate Reynolds numbers. In addition, the positioning of the UV lamp in the reactor plays an important role in determining the RED of the reactor. Search criteria for lamp-positioning are also proposed in the current work. The proposed CFD methodology can be used to analyse the performance of closed-conduit reactors for water disinfection by UV.

This work presents a study on asphalt mixtures prepared with different kinds of additives: poly(styrene- co -butadiene- co -styrene), poly(ethylene- co -vinyl acetate), crumb rubber, fibers, zeolites and clays. The aim of this study was to determine the influence of inorganic dirt and fibers present in crumb rubber on the qualitative parameters of asphalt mixtures. The experiments showed that dynamic viscosity is the best criterion for assessing the effectiveness of the additives in asphalt mixtures. It was also found that fibers and inorganic impurities present in crumb rubber at low concentrations have a negligible effect on the characteristics of asphalt mixtures. This investigation is important in terms of determining the degree of crumb rubber devulcanization in crumb rubber-asphalt mixtures as higher crumb rubber devulcanization could bring the properties of such a mixture closer to those of asphalts modified by poly(styrene- co -butadiene- co -styrene) copolymers.

The influence of the chemical modification of carbon nanotubes on the mechanical, thermal and electrical properties of poly(butylene terephthalate)-based composites was investigated. Polymer composites based on poly(butylene terephthalate) were obtained via in situ polymerisation or extrusion. Commercially available multi-walled carbon nanotubes (Nanocyl NC7000) at different loadings (mass %: 0.05, 0.25, 1, 2) were used as fillers. The functionalisation process took place under a chlorine atmosphere followed by a reaction with sodium hydroxide. The effect of carbon nanotube modification was analysed according to the changes in the polymer thermal and mechanical properties. An addition of modified carbon nanotubes in the amount of 0.05 mass % improved the mechanical properties of the composites in terms of both Young’s modulus and tensile strength by 5–10 % and 17–30 % compared with composites with unmodified carbon nanotubes and neat poly(butylene terephthalate), respectively. The in situ method of composite preparation was a more effective technique for enhancing the matrix–filler interactions, although a significantly lower amount of fillers were used than in the extrusion method.

The analysis of the antioxidant activity of ethanol, methanol, acetone and aqueous extracts from the dried leaves and stems of savory is presented. The culinary herb used to study was procured from ecological agriculture in the Podlasie region of Poland. The antioxidant properties of extracts were calculated using the 1,1-diphenyl-2-picryl-hydrazyl radical (DPPH) and ferric-reducing antioxidant power (FRAP) (expressed as mg Trolox per g of dry mass) methods. In addition, the total phenolics contents of the herbal extracts were determined using the Folin–Ciocalteu reagent. The antioxidative activity of extracts as dependent on the type of solvent used for the extraction and concentration of savory in extracts is discussed. The influence of the concentration of different metal ion solutions on the anti-radicals’ properties of savory extracts was evaluated.

Since chitosan and its amino-, cinnamo- or cinnamo-amino- derivatives are acid-soluble, the effect of acetic acid on hyaluronan (HA) macromolecules degraded by Cu(II) ions and ascorbate was examined to produce reactive oxygen species (ROS). Further, the effects of glutathione (GSH), chitosan and its derivatives, added individually or in combination, on the quenching of ROS and ABTS •+ cation radical were examined using rotational viscometry and ABTS assay, respectively. The results of the rotational viscometry indicated a rapid degradation of HA by ROS after the addition of acetic acid. Chitosan and its derivatives moderately decreased the rate of HA degradation, while GSH decreased the rate of HA degradation more significantly. Moreover, GSH enhanced the protection of HA macromolecules against their degradation in the presence of chitosan or its derivatives. The results of the ABTS assay confirmed the results of the rotational viscometry. The GSH in the combination with chitosan and its derivatives reduced ABTS •+ more intensively than when added individually.

New formulations capable to enhance piroxicam (PRX) water solubility and at the same time to control and adjust its release have been developed. For this purpose, two methods have been used and combined to achieve this goal, namely complexation and microencapsulation by O/W emulsion solvent evaporation. In order to modify the drug release, first, microparticles composed of pure PRX and ethylcellulose (EC) or mixtures of EC and hydroxypropylmethylcellulose (HPMC) were prepared, and then, other micropaticles containing the,β-cyclodextrin/piroxicam (,β-CD/PRX) complex obtained by the solvent evaporation technique and EC or a mixture of EC and HPMC were produced and tested. These formulations were characterized by FT-IR, XRD, optical microscopy, and SEM methods. Drug dissolution tests were carried out in acidic media at pH = 1.2 and 37 °C. Depending on the microparticles composition, their size (dio) ranged between 49 pm and 121 pm and PRXioaded varied from 10.8 % to 27.7 %. The effect of complexation and HPMC polymer on the drug release was investigated; the results demonstrated that the Higuchi’s release constant significantly increased when using the EC/HPMC mixture as a matrix with pure PRX or only EC as a matrix with the ,β-CD/PRX complex. The results are remarkably promising since the combination of these processes provided new SD-CR formulations of piroxicam which enabled simultaneous enhancement and control of its release from the carriers.

The present study used differential scanning calorimetry, thermogravimetric analysis, and UV spectrometry to examine: i) the encapsulation of an organic UV filter 1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione (avobenzone) within modified dextrin and ii) the characteristics of these inclusion complexes (MDA). The properties of avobenzone emulsions with and without encapsulation in modified dextrin, the in vitro UV protection factor, dissolution and release, and the skin penetrability of avobenzone were also examined. The presence of inclusion complexes significantly decreased the tendency of the UV filter to penetrate the skin. In addition, such inclusion complexes should effectively prevent skin damage from radiation extending from the UVA to the UVC.

Glycerol, a liquid matrix material for matrix-assisted laser desorption ionization mass spectrometry, was irradiated by a tunable pulsed infrared laser at wavelengths of 2.80 μm, 2.94 μm, 3.10 μm and 3.50 μm, covering the OH and CH stretch vibrations. A fast photography system was introduced to analyze the dynamic process of plume propagation induced by laser ablation up to 1000 μs of the delay time. Propagation distance of the plume front was measured and the corresponding velocities were calculated; they varied with the wavelength and decreased with the delay time. At the tunable wavelength of the peak of the OH absorption (3.0 μm), theoretical calculations indicate that energy deposition from the pulsed laser is in the regime of stress confinement. The mode of energy deposition depends on the wavelength of the OH vibration and its distance from the absorption maxima. However, stages after a 10 μs delay at various wavelengths show a certain similarity in the distance of plume propagation, which can be well fitted by a drag model.

Benzophenone-3 (BP-3), as an important organic UV filter, is widely used in the sunscreen, cosmetic, and personal care products. The chemical reaction mechanism and kinetics of BP-3 degradation initiated by hydroxyl (OH) radical was investigated in the atmosphere based on the density functional theory (DFT). The results showed that the OH radical is more easily added to the C3 position of the aromatic ring (pathway 3), while the H atom abstraction from the OH group on the aromatic ring (pathway 23) is an energetically favorable reaction pathway. At ambient temperature, 298 K, the overall rate constant for the primary reaction is about 1.50 × 10 −10 cm 3 mol −1 s −1 with the lifetime of 1.92 h. OH addition reactions play the key role in the OH-initiated reaction of BP-3. The study is helpful for better understanding of the removal, transformation, and fate of BP-3 in the atmosphere.