Dithiols as more effective than monothiols in protecting biomacromolecules from free-radical-mediated damage: in vitro oxidative degradation of high-molar-mass hyaluronan

Oxidative stress and the resulting damage to cellular and extracellular components has been observed in a variety of degenerative processes, including degenerative joint disorders, where high-molar-mass hyaluronan (HA) is often found to be massively degraded. The present study sought to test the hypothesis that dithiols are more effective in protecting biomacromolecules from free-radicalmediated damage than monothiols. The materials/thiols tested included bucillamine (BUC), dithioerythritol (DTE), dithiothreitol (DTT) and glutathione (GSH), as a reference, for their effectiveness in protecting HA from oxidative degradation induced in vitro. Since HA degradation results in a decrease in its dynamic viscosity, rotational viscometry was applied to follow HA oxidative degradation. The free-radical-scavenging activities of the thiols tested were determined by 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) and di(phenyl)-(2,4,6-trinitrophenyl)iminoazanium (DPPH) assays. It was found that all the dithiols in the concentration range tested protected HA from the oxidative degradation. On the other hand, monothiol GSH exerted protection only at high concentrations (10 μmol L^?1 and 100 μmol L^?1) and 1 μmol L^?1 of GSH even exhibited a prodegradative effect. The ABTS assay revealed free-radical scavenging activities in the following order: BUC, DTT, DTE, GSH, and that of the DPPH assay: BUC, DTE, DTT, GSH. In conclusion, it was demonstrated that dithiols may be more effective than monothiols in affording biomacromolecule protection from oxidative degradation.     

Radical-scavenging activity of glutathione,chitin derivatives and their combination

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.     

The endomorphism spectrum of a monounary algebra

The endomorphism spectrum specA of an algebra A is defined as the set of all positive integers, which are equal to the number of elements in an endomorphic image of A, for all endomorphisms of A. In this paper we study finite monounary algebras and their endomorphism spectrum. If a finite set S of positive integers is given, one can look for a monounary algebra A with S = specA. We show that for countably many finite sets S, no such A exists. For some sets S, an appropriate A with spec A = S are described. For n ∈ ? it is easy to find a monounary algebra A with {1, 2, ..., n} = specA. It will be proved that if i ∈ ?, then there exists a monounary algebra A such that specA skips i consecutive (consecutive eleven, consecutive odd, respectively) numbers. Finally, for some types of finite monounary algebras (binary and at least binary trees) A, their spectrum is shown to be complete.     

Removal of selected chlorinated micropollutants by ozonation

Feasibility of ozone oxidation for the elimination of selected dissolved organic micropollutants from water and wastewaters was studied. Five organochlorine pesticides, i.e. hexachlorobutadiene, pentachlorobenzene, hexachlorobenzene, lindane, and heptachlor, were used as organic contaminants of model water. The first four of them are classified as priority hazardous substances. The oxidation treatment process was performed in a jet loop reactor. Ozone was prepared from pure oxygen. Quantification of the organochlorine pesticides in water was achieved by the gas chromatographic method after liquid-liquid extraction. Significant contribution of stripping to the removal of the investigated compounds during the ozonation treatment was also proven by the results. Effective ozonation time with regard to treatment efficiencies was 30 min, which corresponds to the ozone input of 317 mg per liter of active volume of the ozonation reactor. Single power law kinetic models were used to describe experimental data and kinetic parameters were estimated. The best fit of the experimental degradation data of all studied pollutants was obtained by the second order kinetic model. It can be concluded, based on the results obtained, that the applied ozonation process is a promising procedure for the removal of the investigated pesticides from aquatic environment.     

Synthesis,thermal, spectral and biological properties of zinc(II) 4-hydroxybenzoate complexes

New zinc(II) 4-hydroxybenzoate complex compounds with general formula [Zn(4-OHbenz)₂L_n]·xH₂O, where 4-OHbenz = 4-hydroxybenzoate; L = isonicotinamide, N-methylnicotinamide, N,N-diethylnicotinamide, thiourea, urea, phenazone, theophylline, methyl-3-pyridylcarbamate; n = 2, 3; x = 0–3, 5, were synthesized and characterised by elemental analysis, thermal analysis and IR spectroscopy. The thermal behaviour of the prepared compounds was studied by TG/DTG and DTA methods in argon atmosphere. The thermal decomposition of hydrated compounds started with dehydration. During the thermal decomposition, organic ligand, carbon monoxide, carbon dioxide and phenol were evolved. The final solid product of the thermal decomposition was zinc or zinc oxide. The volatile gaseous product, solid intermediate products and the final product of thermal decomposition were identified by IR spectroscopy, mass spectrometry, qualitative chemical analyses and X-ray powder diffraction method. The antimicrobial activity of zinc(II) carboxylate compounds was tested against various strains of bacteria, yeasts and filamentous fungi (S. aureus, E. coli, C. parapsilosis, R. oryzae, A. alternata, M. gypseum). The presence of zinc in complexes led to the increase in their antimicrobial activity in comparison with free 4-hydroxybenzoic acid.     

DNA-based biosensors with external Nafion and chitosan membranes for the evaluation of the antioxidant activity of beer,coffee, and tea

Novel electrochemical DNA-based biosensors with outer-sphere Nafion and chitosan protective membranes were prepared for the evaluation of antioxidant properties of beverages (beer, coffee, and black tea) against prooxidant hydroxyl radicals. A carbon working electrode of a screen-printed three-electrode assembly was modified using a layer-by-layer deposition technique with low molecular weight double-stranded DNA and a Nafion or chitosan film. The membrane-covered DNA biosensors were initially tested with respect to their voltammetric and impedimetric response after the incubation of the beverage and the medium exchange for the solution of the redox indicator [Fe(CN)₆]^3?/4?. While the Nafion-protected biosensor proved to be suitable for beer and black tea extracts, the chitosan-protected biosensor was successfully used in a coffee extract. Afterwards, the applicability was successfully verified for these biosensors for the detection of a deep degradation of the surface-attached DNA at the incubation in the cleavage agent (hydroxyl radicals generated via Fenton reaction) and for the evaluation of antioxidant properties of coffee and black tea extracts against prooxidant hydroxyl radicals. The investigation of the novel biosensors with a protective membrane represents a significant contribution to the field of electrochemical DNA biosensors utilization.      

An Improved Method for Determination of Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers in Sediment by Ultrasonic Solvent Extraction Followed by Stir Bar Sorptive Extraction Coupled to TD–GC–MS

An improved simple, fast and miniaturized method for the determination of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in freshwater sediment using ultrasonic solvent extraction followed by stir bar sorptive extraction–thermal desorption–gas chromatography–mass spectrometry (USE-SBSE/TD–GC–MS) is presented. The sediment sample (0.2 g) is extracted with methanol (1:1.2, 2:1.0 mL) in an ultrasonic bath (two 5-min extraction cycles). The combined extracts are made up to 5 mL with water, and from the resulting solution, the analytes are preconcentrated on a stir bar coated with polydimethylsiloxane during 1 h of stirring. The loaded sorptive stir bar is then thermally desorbed and online analysed by GC–MS. For the analytes in river sediment, a linear dynamic range of 0.5–50 ng g^?1 was established and limits of detection in sub nanogram-per-gram level were achieved. Recoveries and repeatability were obtained in the ranges 62.8–91.5 % and 3.6–15.0 %, respectively. The method accuracy was confirmed by the analysis of PCBs and PBDEs in a certified reference material. The main improvement in comparison with similar published methods is in shortening the sample handling time and the method miniaturization.     

A Note on Invariant Observables

The ergodic theory and particularly the individual ergodic theorem were studied in many structures. Recently the individual ergodic theorem has been proved for MV-algebras of fuzzy sets (Riečan, 2000; Riečan and Neubrunn, 1997) and even in general MV-algebras (Jurečková, 2000). The notion of almost everywhere equality of observables was introduced by B. Riečan and M. Jurečková in Riečan and Jurečková (2005). They proved that the limit of Cesaro means is an invariant observable for P-observables. In this paper show that the assumption of P-observable can be omitted.     

Synthesis of Pyrazoloazepines from 5-Aminopyrazoles and Study of Their Cytotoxicity in Cancer Treatment

The novel synthetic approach was employed to synthesize a series of 1,8-dihydropyrazolo[3,4-b]azepine derivatives from 5-aminopyrazoles in three-step synthesis. The structures of the individual derivatives were unambiguously confirmed by spectral methods, including heteronuclear ¹H−¹³C HMBC spectra and other necessary 2D NMR experiments. The obtained pyrazoloazepines and starting aminopyrazoles were subsequently investigated for their potential cytotoxic effect using mouse and human leukemia cell models. The original L1210 (mouse lymphoblastic), MOLM-13, and SKM-1 (both human myeloblastic) cell lines and their P-glycoprotein (P-gp) expressing cell variants were used. Aminopyrazole 8 was the most effective on murine leukemic lymphoblasts (L1210), while it had a greater effect on P-gp expressing cells. In contrast, on human leukemic myeloblasts (MOLM-13, SKM-1), Aminopyrazoles 10 showed the most pronounced effect, but this was independent of the presence of P-gp in the cells.