Electroanalytical Techniques for the Detection of Selenium as a Biologically and Environmentally Significant Analyte—A Short Review

This short review deals with the properties and significance of the determination of selenium, which is in trace amounts an essential element for animals and humans, but toxic at high concentrations. It may cause oxidative stress in cells, which leads to the chronic disease called selenosis. Several analytical techniques have been developed for its detection, but electroanalytical methods are advantageous due to simple sample preparation, speed of analysis and high sensitivity of measurements, especially in the case of stripping voltammetry very low detection limits even in picomoles per liter can be reached. A variety of working electrodes based on mercury, carbon, silver, platinum and gold materials were applied to the analysis of selenium in various samples. Only selenium in oxidation state + IV is electroactive therefore the most of voltammetric determinations are devoted to it. However, it is possible to detect also other forms of selenium by indirect electrochemistry approach.     

A general procedure for the dynamic analysis of finite and infinite beams on piece-wise homogeneous foundation under moving loads

Transversal vibrations induced by a load moving at a constant speed along a finite or an infinite beam resting on a piece-wise homogeneous visco-elastic foundation are studied. Special attention is paid to the amplification of the vibrations which arise as the point load traverses a foundation discontinuity. The governing equations of the problem are solved by the normal-mode analysis. The solution is expressed in the form of an infinite sum of orthogonal natural modes multiplied by the generalized displacements. The natural frequencies are obtained numerically exploiting the concept of the global dynamic stiffness matrix. This ensures that the frequencies obtained are accurate. The methodology is neither restricted by load velocity nor damping and is simple to use, though obtaining the numerical expression of the results is not straightforward. A general procedure for numerical implementation is presented and verified. There is no restriction for finite structures, however, for infinite structures, validity of the results is restricted to a “region of interest” of finite length. To illustrate the methodology, the probability of exceeding an admissible upward displacement is determined when the load travels at a certain velocity according to the normal distribution. In this problem, the given structure has an intermediate part of adaptable foundation stiffness, which is optimized in a parametric way, enabling to draw important conclusions about the optimum intermediate stiffness. The results obtained have direct application on the analysis of railway track vibrations induced by high-speed trains crossing regions with significantly different foundation stiffness.     

Study of carbon black obtained by pyrolysis of waste scrap tyres

Waste scrap tyres were thermally decomposed under various conditions. Decompositions were followed by the TGA method. Specific heating regimes were tested to obtain optimal structural properties of resulting pyrolytic carbon black produced by pyrolysis of scrap tyres and the process was characterized in temperature interval from 380 to 1,200 °C and heating rate 10, 20 and 50 °C min^?1 under nitrogen atmosphere. The original scrap tyres and pyrolytic carbon black were characterized by Raman and Fourier transform infrared spectroscopy methods. Textural properties were also determined. Effect of temperature and heating rate on process of pyrolysis of scrap tyres was observed. Shifting of temperature of maximum pyrolysis rate to lower value and spreading of DTG peak is caused by increasing heating rate. Temperature 570 °C was sufficient for total scrap tyres pyrolysis. Graphitic and disordered structure was distinguished in the formed carbon black by Raman spectroscopy. With increasing temperature, heating rate and weight loss, the amount of the graphitic structure was reduced at the expense of disordered structure. Destruction of nonporous scrap tyres and formation of porous structure took place at higher temperature. Porous carbon black is formed above 380 °C, specific surface area increased up to 88 m² g^?1 .     

Offline and online capillary electrophoresis enzyme assays of β-N-acetylhexosaminidase

Enzyme assays of β-N-acetylhexosaminidase from Aspergillus oryzae using capillary electrophoresis in the offline and online setup have been developed. The pH value and concentration of the borate-based background electrolyte were optimized in order to achieve baseline separation of N,N′,N″-triacetylchitotriose, N,N′-diacetylchitobiose, and N-acetyl-d-glucosamine. The optimized method using 25 mM tetraborate buffer, pH 10.0, was evaluated in terms of repeatability, limits of detection, quantification, and linearity. The method was successfully applied to the offline enzyme assay of β-N-acetylhexosaminidase, which was demonstrated by monitoring the hydrolysis of N,N′,N″-triacetylchitotriose. The presented method was also utilized to study the pH dependence of enzyme activity. An online assay with N,N′-diacetylchitobiose as a substrate was developed using the Transverse Diffusion of Laminar Flow Profiles model to optimize the injection sequence and in-capillary mixing of substrate and enzyme plugs. The experimental results were in good agreement with predictions of the model. The online assay was successfully used to observe the inhibition effect of N,N′-dimethylformamide on the activity of β-N-acetylhexosaminidase with nanoliter volumes of reagents used per run and a high degree of automation. After adjustment of background electrolyte pH, an online assay with N,N′,N″-triacetylchitotriose as a substrate was also performed.

Comparison of different types of outlet frits in slurry‐packed capillary columns

Fused‐silica capillary columns for high‐performance liquid chromatography with 320 and 250 μm inner diameter were prepared by slurry packing with 5 and 3 μm Nucleosil C₁₈ stationary phase. Different types of mechanical and monolithic outlet frits were used and their influence on the resulting column performance was evaluated. Columns with quartz wool exhibited symmetrical peaks and low theoretical plate height, and the preparation time was short. The performance of monolithic frits varied based on type of monolith, length of the frit, and silanization procedure. The best frit performed similarly to the quartz wool ones, but the preparation took several hours. Their main advantage lies in the possibility of on‐column detection, because the detection window can be burnt immediately behind the frit.     

Need for database extension for reliable identification of bacteria from extreme environments using MALDI TOF mass spectrometry

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 ?iar 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.     

Ethylene Induction of Non-Enzymatic Metabolic Antioxidants in Matricaria chamomilla

Phytochemical investigations of Matricaria chamomilla L. (Asteraceae) stated the presence of several compounds with an established therapeutic and antioxidant potential. The chamomile non-enzymatic antioxidant system includes low molecular mass compounds, mainly polyphenols such as cinnamic, hydroxybenzoic and chlorogenic acids, flavonoids and coumarins. The objective of this work was to evaluate the role of the non-enzymatic antioxidant system after stimulation by ethylene in tetraploid chamomile plants. Seven days of ethylene treatment significantly increased the activity of phenylalanine ammonia-lyase, which influenced the biosynthesis of protective polyphenols in the first step of their biosynthetic pathway. Subsequently, considerable enhanced levels of phenolic metabolites with a substantial antioxidant effect (syringic, vanillic and caffeic acid, 1,5-dicaffeoylquinic acid, quercetin, luteolin, daphnin, and herniarin) were determined by HPLC-DAD-MS. The minimal information on the chlorogenic acids function in chamomile led to the isolation and identification of 5-O-feruloylquinic acid. It is accumulated during normal conditions, but after the excessive effect of abiotic stress, its level significantly decreases and levels of other caffeoylquinic acids enhance. Our results suggest that ethephon may act as a stimulant of the production of pharmaceutically important non-enzymatic antioxidants in chamomile leaves and thus, lead to an overall change in phytochemical content and therapeutic effects of chamomile plants, as well.