Band 60, Heft 3

The possibility of calibrationless chronoamperometric determination is described using a pair of individually addressable and diffusion layers interacting segments of interdigitated microelectrode array (IDA). It utilizes dual voltammetric mode where the first segment is polarized with potential corresponding to the limiting current of determined species electrode reaction and the second segment is polarized with potential corresponding to the opposite electrode reaction limiting current. Time at which the current of the collector segment reaches one half of the steady state is hyperbolically dependent on the diffusion coefficient of analyte. The determination of diffusion coefficient allows direct calculation of bulk concentration avoiding calibration with a standard solution. The equipment for measuring of fast response of IDA arrays in dual mode has been developed using a bipotentiostat connected with A/D transducer. It allows less than 1 ms sampling period for ultrafast registration of chronoamperogram. The method was tested and validated with [Fe(CN)6]4−, [Ru(NH3)6]Cl3, and ferrocene model samples using various types of IDA arrays.

The apparently unpredictable behaviour of β-carotene in the supplementation of the diet of smokers is discussed in the light of the reactions of peroxyl radicals with β-carotene in the absence of oxygen. The decay of tert-butylperoxyl radicals in the presence of β-carotene was studied at ambient temperature in non-polar solvents by ESR spectroscopy. The primary reaction in the absence of oxygen is interpreted as a spin-trapping effect of a peroxyl radical by β-carotene producing an intermediate labile free radical, which disappears after recombination with a second tert-butylperoxyl radical. The result is the transformation of β-carotene to a diamagnetic compound with two peroxy bonds. In the presence of chelating transition metals with unpaired d-electrons as electron donors the peroxy group of the oxidized β-carotene can be split to alkoxyl free radicals. The primary attack of tert-butylperoxyl radicals is completely inhibited in the presence of vitamin E followed by production of free aryloxy radicals and the presence of oxygen has no significant effect on this reaction. Spin-trapping of peroxyl radicals by the double bond of vitamin A leads to its oxidation in the absence of vitamin E. Transition metal ions such as Co, Cr, Fe, and Mn, known to be present in the aerosol of cigarette smoke, homolyse the peroxyl bonds of peroxidised β-carotene, which results in cell damage.

The quality and authenticity of commercially available honey from Slovak market and the development of HPLC method for determination of hydroxymethylfurfural (HMF) content of honey with fine separation efficiency, sensitivity, applicability, and recovery was evaluated. Physicochemical parameters (moisture, total acidity, content of proline, saccharides, and value of electrical conductivity) have been determined.

In pH 3.5 Britton—Robinson buffer solution double-stranded (ds) DNA can react with malachite green (MG) to form an interaction complex, which resulted in the decrease of the electrochemical response of MG, MG had a well-defined second-order derivative linear sweep voltammetric peak at −0.73 V (vs. SCE). After the addition of dsDNA into MG solution, the reductive peak current decreased with the positive shift of peak potential, which was the typical characteristic of intercalation. Based on the interaction, an indirect electrochemical determination method for dsDNA was established. The optimum conditions for the reaction were investigated and there were little or no interferences from the commonly coexisting substances. The decrease of peak current was linear with the concentration of dsDNA over the range of 0.8–12.0 µg cm−3 with the linear regression equation as ΔI p″/nA = 91.70 C/(µg cm−3) + 74.55 (n = 10, γ = 0.990). The detection limit was calculated as 0.46 µg cm−3 (3σ). The method had high sensitivity and was further applied to the dsDNA synthetic samples with satisfactory result. The interaction mechanism was discussed with the intercalation of DNA-MG to form a supramolecular complex and the stoichiometry of the supramolecular complex was calculated by electrochemical method with the binding number 3 and the binding constant 2.35 × 1015 (mol dm−3)−3.

The tetranuclear Cu4OBrnCl(6−n)(pm)4 complexes, where pm = 3-pyridylmethanol (3-pm), 4-pyridylmethanol (4-pm) and n = 0−6 with trigonal bipyramidal coordination of copper(II) were prepared and their infrared and electronic absorption spectra as well as cyclic voltammograms in nitromethane solutions were measured. The molecules exhibit strong single infrared Cu4O stretching absorptions between 580 and 530 cm−1 which are in linear correlations with the number of halides, n. Far infrared absorptions assigned to Cu-Br, Cu-Cl, and Cu-N stretching vibrations appear at higher wavenumbers for 3-pm complexes compared with those for 4-pm complex molecules. Two strongly overlapped d–d bands in the region 11300–13100 cm−1 assigned to $$e(d_{x^2 - y^2 } ,d_{xy} ) \to a_1 (d_{z^2 } )$$ and e(d xz, d yz) → a 1(d z 2) transitions in the trigonal bipyramidal coordination of the copper(II) atoms were resolved by Gaussian analysis. Both, 3-pm and 4-pm ligands produce in the complex molecules almost the same ligand field. The maxima of the Gaussian d–d components vary with the parameter n and are for both series of the complexes deviated from linearity, more for the low-energy d–d bands than for high-energy analogues. The electrochemical reduction in nitromethane is significantly less reversible for 4-pm complex molecules compared with that of 3-pm analogues. Formal reduction potentials E′ c for 3-pm complexes were observed in the range 478 (n = 0)−599 (n = 6) mV. The plot E′ c vs. n is significantly deviated from linearity. It is suggested that the reducing electrons enter the half-filled d z 2 orbital of the copper(II) atom. The different spectral and electrochemical results obtained for 3-and 4-pm complexes are explained by different structural distortions, bond lengths, and charge distributions produced by halide ligand variations. The results are also discussed with previously reported data on analogous pyridine, 3-methylpyridine and 4-methylpyridine complexes.

Some physicochemical properties of 2-chloro-4-nitrobenzoates of Co(II), Ni(II), and Cu(II) were studied. The complexes were obtained as mono-and dihydrates with a metal ion—ligand mole ratio of 1: 2. All complexes are polycrystalline compounds. Their colours depend on the kind of central ion: pink for Co(II) complex, green for Ni(II), and blue for Cu(II) complexes. Their thermal decomposition was studied only in the range of 293 K–523 K because it was found that on heating in air above 523 K 2-chloro-4-nitrobenzoates decompose explosively. Hydrated complexes lose crystallization water molecules in one step. During dehydration process no transformation of the nitro group to nitrito one took place. Their solubilities in water at 293 K are of the orders of 10−3-10−2 mol dm−3. The magnetic moment values of 2-chloro-4-nitrobenzoates determined in the range of 76 K–303 K change from 3.48µB to 3.82µB for Co(II) complex, from 2.24µB to 2.83µB for Ni(II) 2-chloro-4-nitrobenzoate, and from 0.31µB to 1.41µB for Cu(II) complex. 2-Chloro-4-nitrobenzoates of Co(II) and Ni(II) follow the Curie—Weiss law, but the complex of Cu(II) forms dimer.

A new 4-[1-(4-methylphenylsulfonyl)-1H-indol-3-yl]but-3-en-2-one thiosemicarbazone (HL) was synthesized derived from 4-[1-(4-methylphenylsulfonyl)-1H-indol-3-yl]but-3-en-2-one. Four transition metal(II) complexes of HL have been prepared. Elemental analysis, molar conductivity, IR, UV, 1H NMR spectra, and TG-DTA have been used to characterize these complexes. The complexes have the general formula ML2, where M = Zn, Cu, Co, and Ni. The ligand and its complexes have been studied for their possible biological activity including anti-inflammatory, antibacterial, and antitumour activity in vitro.

The crystal structure of 2-(2,4-dimethylanilino)-3-methyl-6-diethylaminofluorane has been determined by single crystal X-ray diffraction method. The crystal belongs to triclinic system, space group P-1 with unit cell constants a = 11.2877(9) Å, b = 11.9539(9) Å, c = 12.2365(9) Å, α = 97.2580(10)°, β = 116.2850(10)°, γ = 106.3710(10)°, V = 1358.48(18) Å 3, Z = 2, D c = 1.234 g/cm3, μ = 0.079 mm−1, F(000) = 536, R and w(R) are 0.0718 and 0.2055, respectively, for 5239 unique reflections with 3745 observed reflections (I > 2σ(I)).

The reaction of glycerol with tert-butyl alcohol in the liquid phase on acid Amberlyst-type ion-exchange resins was studied. The influence of temperature, mole ratio n(TBA)/n(G), water and swelling of gel, and macroreticular type of polymer catalysts on etherification reaction was investigated. The most favourable reaction temperature is 75°C. The conversion of glycerol and yield of glycerol tert-butyl ethers has increased with the mole ratio n(TBA)/n(G). Dry form of macroreticular catalysts provided the best results. Etherification reaction of glycerol with isobutylene in non-aqueous conditions gives the highest yield of desired ethers. The influence of water was studied. The gel forms of ion-exchange resins have very low catalytic activity. It can be concluded that water has an inhibition effect on ion-exchange resins. By comparing the gel and macroreticular forms of Amberlyst ion-exchange resins it can be concluded that very acid forms of macroreticular ion-exchange resins with a high degree of crosslinking are more active catalysts for the studied reaction due to their pores which are sufficiently large so that the voluminous tert-butyl ethers of glycerol can be formed. It was estimated that tert-butyl alcohol as tert-butylation agent is not suitable for etherification of glycerol with the formation of di-and triethers.

Substituted furopropenoic acids were prepared from appropriate aldehyde under the Doebner’s conditions. Obtained acids were converted to the corresponding azides, which were cyclized by heating in Dowtherm to furopyridones. These compounds were aromatized with phosphorus oxychloride to chloro derivatives of furo[3,2-c]pyridine (Va, Vb). Chloro derivative Vb was reduced with hydrazine hydrate to 2-(4-aminophenyl)furo[3,2-c]pyridine in ethanol and Pd/C as a catalyst. Chloro derivative Va was converted to 4-amino-2-(3-pyridyl)furo[3,2-c]pyridine under the same conditions. The chlorine atom in other chloro derivatives (VIIa, VIIb) was replaced by nucleophilic substitution with alkoxides (sodium ethoxide, propoxide, and isopropoxide) and the corresponding alkoxy derivatives were formed. By reaction of VII with cyclic secondary amines (morpholine, piperidine, and pyrrolidine) 4-substituted furopyridines were prepared.

1,3-Dipolar cycloaddition reaction of bis{[4-(3,4-dihydro-(2H)-naphthalen-1-oxo-2-yl)methyl-idenephenyl]oxy}alkanes with nitrilimines (generated in situ by triethylamine dehydrohalogenation of the corresponding hydrazonoyl chlorides) in refluxing dry benzene afforded a mixture of monocycloadduct and dicycloadduct products in high regioselectivity. On the other hand, reaction of bis{[2-(3,4-dihydro-(2H)-naphthalen-1-oxo-2-yl)methylidenephenyl]oxy}alkanes with nitrilimines gave the corresponding dicycloadducts as the only isolable regioisomers.

The structure of the cell wall glucan isolated from the industrial strain of Saccharomyces cerevisiae was characterized as to be composed of a linear (1→3)-β-D-glucan chain with single β-D-glucopyranosyl residues attached to every ninth backbone unit by (1→6)-glycosidic linkages. Mild oxidation of this β-D-glucan with a dimethyl sulfoxide—acetic anhydride reagent yielded an “oxidized” glucan with aldehyde groups introduced at C-6 and carbonyl oxygens located at C-2 and C-4 of the glucopyranosyl rings. The conversion of the oxidized glucan into the polyoxime was used to study the progress of oxidation and to establish the carbonyl groups distribution in this new reactive polysaccharide derived from baker’s yeast cell wall.

Complex polymer systems, which exhibit multiple distributions in their molecular parameters can be characterized by coupled liquid chromatographic methods. The latter combine entropic (exclusion) and enthalpic (interaction) retention mechanisms. However, recent experimental results suggest that some coupled liquid chromatographic methods may suffer from incomplete sample recovery. This refers, for example, to liquid chromatography under critical conditions of enthalpic interactions and to eluent gradient liquid chromatography. Sample recovery in both latter methods was investigated for selected model systems applying adsorption retention mechanism. Reduced sample recovery was confirmed for both methods. It was revealed that even very high final strength of mobile phase may be insufficient for complete elution of polymer samples in eluent gradient polymer liquid chromatography.