Band 63, Heft 4

Volatiles of fresh flowers of Prunus domestica L. and Prunus padus L. (their diethyl ether extracts) were analyzed by GC and GC-MS. 110 and 33 constituents were identified in P. domestica and P. padus extracts, respectively. 32 of the identified constituents were previously unreported as metabolites of taxa belonging to the genus Prunus. Six of them (4-methoxybenzyl palmitate, isoamyl stearate, isoamyl eicosanoate, isoamyl docosanoate and penta-O-acetyl-α- and β-D-glucopyranoses) are compounds reported for the first time from a natural source and one (isoamyl tetracosanoate) is a new compound in general. The major component of P. domestica extract was kaempferol (35.0 %), while P. padus extract was found to be rich in (Z)-8-hydroxylinalool (30.4 %), benzaldehyde (19.8 %) and 2-phenylethanol (15.1 %). Both extracts (P. domestica and P. padus) contained rather large amounts of shikimate metabolites (51.7 % and 39.1 %, respectively) and anther related odd-carbon numbered alkanes (23.2 % and 27.0 %, respectively). The observed differences between P. domestica and P. padus extracts corroborate the placement of P. domestica and P. padus in separate subgenera (Prunus and Cerasus, respectively) of the genus Prunus.

A simple, selective and sensitive kinetic method for the determination of nitrite in water was developed. The method is based on the catalytic effect of nitrite on the oxidation of methylene blue (MB) with bromate in a sulfuric acid medium. During the oxidation process, absorbance of the reaction mixture decreases with the increasing time, inversely proportional to the nitrite concentration. The reaction rate was monitored spectrophotometrically at λ = 666 nm within 30 s of mixing. Linear calibration graph was obtained in the range of 0.005–0.5 μg mL−1 with a relative standard deviation of 2.09 % for six measurements at 0.5 μg mL−1. The detection limit was found to be 0.0015 μg mL−1. The effect of different factors such as acidity, time, bromate concentration, MB concentration, ionic strength, and order of reactants additions is reported. Interference of the most common foreign ions was also investigated. The optimum experimental conditions were: 0.38 mol L−1 H2SO4, 5 × 10.4 mol L−1 KBrO3, 1.25 × 10.5 mol L−1 MB, 0.3 mol L−1 sodium nitrate, and 25°C. The proposed method was conveniently applied for the determination of nitrite in spiked drinking water samples.

Diverse recombinant immunoreagents specific for TNT-derivatives were tested in different assay forms in order to analyze their specificity and sensitivity. Performance of immunoassays was based on TNP-protein conjugates immobilization on a solid surface. In this work, the detection limit for TNT-analog TNP-Tris was 250 fmol or 87 pg mL−1 (87 ppt), which represents the most sensitive assay published until now, regarding the detection of recombinant antibodies.

Complex mixtures, particularly petroleum fractions, usually need to be suitably modeled before providing the simulation and other types of chemical engineering calculations. The most convenient way is to describe the original mixture by a substitute mixture. The formerly published approach based on the employment of substitute mixtures of real components can be improved in order to get a closer match between the behavior of the original and substitute mixtures. In the first phase of the algorithm, a new concept of a band around the characterization curves brings wider possibilities for the selection of real components into the substitute mixture. The second phase, which is used to determine the composition of the substitute mixture, can be also improved by considering the global or bulk properties of the original mixture if available. Typically, some of the properties e.g. liquid density, molecular mass and PNA (Paraffinic/Naphthenic/Aromatic carbon) analysis can be measured and used to improve the adjustment of the composition. The improved algorithm is illustrated by an example.

Oil pumpkin (Cucurbita pepo L. var. Styriaca) is an economically important horticultural plant cultivated for oil production. After harvesting seeds, the residual biomass has a limited application and is usually left in the field. An experimental study was performed to evaluate the chemical composition of the seeded fruit oil pumpkin biomass (OP) dried by solvent-exchange using ethanol. The sugar composition of polysaccharides obtained by sequential extraction with water and dilute alkali indicated the prevalence of pectic polysaccharides. Hemicelulloses were released in higher amounts in the alkaline step. The chemical composition of OP and its individual tissues (peel, flesh and hairy flesh) was investigated and compared to the corresponding preparations of standard pumpkin (SP, Cucurbita pepo L.). The content of components (on oven-dry basis), calculated from the analysis data of the individual tissues, was estimated for OP: 7.9 % ash, 7.6 % Klason lignin, 19.3 % pectin (as uronic acids), 34.1 % neutral carbohydrates, and 27.4 % α-cellulose and for SP: 6.4 % ash, 4.0 % Klason lignin, 20.9% pectin (as uronic acids), 38.1% neutral carbohydrates, and 29.2 % α-cellulose, respectively. The OP biomass showed a higher proportion of hemicelluloses.

Application of 31P NMR for qualitative and quantitative determination of added phosphorus compounds in meat samples is described. Furthermore, usefulness of the proposed method for monitoring of poly- and pyrophosphates hydrolysis in meat is discussed. Calibration curves based on the 31P resonance line areas were elaborated for Na3P3O9, Na5P3O10, Na2H2P2O7, and K4P2O7 resulting in linearity (R 2 = 0.9976, 0.9953, 0.9974, and 0.9524, respectively), detection limits (DL from 0.0018 mol L−1 for Na3P3O9 to 0.0070 mol L−1 for K4P2O7), and quantification limits (QL from 0.0060 mol L−1 for Na3P3O9 to 0.0234 mol L−1 for K4P2O7). The developed procedure was applied for laboratory prepared meat samples and compared with the standard UV-VIS method. The minimal sample pretreatment, obtained within-day precision (CV ≤ 2.0 %) and accuracy (as recovery ≥ 95 %) suggest 31P NMR as an alternative method of phosphorus determination in food analysis.

Complexation reactions in a binary metal/phosphate system were studied. Protolytic equilibria of phosphate in the presence of cobalt, nickel, iron, copper, chromium and silver metal ions were investigated by potentiometric titrations in the pH range of 2–11. Stability constants of the metal/phosphate complexes were determined by computer analysis of the potentiometric titration. Potentiometric titrations suggest that the presence of metal phosphate and metal hydrogen phosphate provides the solutions with stability constants logK c 2.21, 2.11, 2.23, 2.34, 1.96, and 2.14 of Co, Ni, Fe, Ag, Cr, and Cu/phosphate, respectively. The results of infrared spectroscopy, X-ray powder diffraction and equilibrium studies were used to reveal the mode of interaction between the metal ions and phosphate. Metal phosphates with a hydrogen phosphate anion and fully nonprotonated phosphate could be isolated under the reaction conditions.

Four transition metal(II) complexes with podophyllic acid hydrazide (HL) were prepared and characterized by elemental analysis, complexometric titration, thermal analysis, conductivity, IR, and 1H NMR. The complexes have the general formula ML2 · nH2O, where M = Zn, Cu, Co, and Ni, n = 2 or 0. Anti-tumor activities of podophyllotoxin, HL, ZnL2 · 2H2O, and NiL2 were tested by both the MTT and the SRB method. The results show that the activities of the complexes against the tumor cells tested are superior to HL and the anti-tumor activity of NiL2 is even similar to that of podophyllotoxin.

An artificial neural network (ANN) model for modeling and prediction of the steric hindrance parameter σ of polymers with three quantum chemical descriptors, the average polarizability of a molecule α, entropy S, and dipole moment μ, was developed. These descriptors were calculated from the monomers of the respective polymers according to the density functional theory at the B3LYP level of the theory with the 6-31G(d) basis set. Optimal conditions were obtained by adjusting various parameters by trial-and-error. Simulated with the final optimum BP neural network [3-1-1], the results show that the predicted σ values are in good agreement with the experimental ones, with the root mean square (rms) error being 0.080 (R = 0.945) for the training set, and 0.078 (R = 0.918) for the test set, which indicates that the proposed model has better predictive capability than the existing one.

Three tetracationic porphyrins differing in the position of charged nitrogen atoms on the peripheral substituents — 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP4), 5,10,15,20-tetrakis(N-methylpyridinium-2-yl)porphyrin (TMPyP2), 5,10,15,20-tetrakis(4-trimethylammoniophenyl) porphyrin (TMAPP), and hydrophobic 5,10,15,20-tetraphenylporphyrin (TPP), were immobilized by adsorption and encapsulation in poly(hydroxymethylsiloxane) (PHOMS). The so prepared porphyrin-PHOMS composites were characterized by porosimetry, scanning electron microscopy, fluorescence and diffuse reflectance UV-VIS spectroscopy. It was found that porphyrins are immobilized in the PHOMS matrix in the free base monomer form Their irradiation produced singlet oxygen O2(1Δg) with the lifetime of 10–30 μs.

Cordierite porous ceramics Z, X, and K were prepared using three mixtures of clay minerals: Z from kaolinite, talc, and aluminum hydroxide, X from kaolinite, talc, vermiculite, and aluminum hydroxide, and K from kaolinite, talc, and magnesium oxide. Ceramics were different in porosity, specific surface area, cordierite polymorphs, and secondary crystalline phases. Vermiculite influenced textural architecture of calcined cordierite ceramics X and predestinated crystallization of the high-temperature hexagonal α-cordierite with secondary minerals enstatite, spinel and corundum. Ceramics Z contained low-temperature orthorhombic β-cordierite, enstatite, and corundum, K was diphase of β-cordierite and forsterite. Total pore area (TPA) and specific surface area (SSA) of X, in spite of the higher porosity and the pore size distribution in the range of 300–1000 nm, were smaller in comparison with TPA and SSA of Z. Ceramics K retained high porosity, two maxima at 300–1000 nm and 50–200 nm in the pores size distribution, and the highest TPA and SSA compared to those observed in ceramics Z and X.

Microwave-induced combustion with glycine, CTAB-assisted hydrothermal process with NaOH and NH3, EDTA assisted-hydrothermal methods have been applied to prepare NiFe2O4 nanoparticles for the first time. Structural and magnetic properties of the products were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmison electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and electron spin resonance spectrometry (EPR). TEM measurements showed that morphology of the product depends on the synthesis method employed. The average cystallite size of NiFe2O4 nanoparticles was in the range of 14–59 nm as measured by XRD. The uncoated sample (Method A) had an EPR linewidth of 1973 Oe, the coated samples reached lower values. The magnetic dipolar interactions existing among the Ni ferrite nanoparticles are reduced by the coatings, which could cause the decrease in the linewidth of the EPR signals. Additionally, the linewidth increases with an increase in the size and the size distribution of nanoparticles.

A series of 1,3-diaryl-2-propen-1-ones and their indole analogs were synthesized and evaluated for antibacterial activity. Structures of newly synthesized compounds were confirmed by physicochemical, spectral and elemental analysis. All the compounds were screened for their antibacterial activities against four different bacterial strains. The QSAR studies were performed using Vlife MDS 3.5 software. QSAR equation revealed that selected electronic, steric and lipophilic parameters have good correlation with antibacterial activity. Best equations were selected on basis of the correlation coefficient (r 2) and the predictable ability of the equations. The present findings suggest that the 1,3-diaryl-2-propen-1-ones framework is an attractive template for structure optimization to achieve higher potency, lower toxicity, and a wider spectrum of antibacterial activity.

In pursuit of better CRTh2 receptor antagonist agents, QSAR studies were performed on a series of 2,4-disubstituted phenoxyacetic acid derivatives. Stepwise multiple linear regression analysis was performed to derive QSAR models which were further evaluated for statistical significance and predictive power by internal and external validation. The best QSAR model was selected; having the correlation coefficient R = 0.904, standard error of estimation SEE = 0.456 and the cross validated squared correlation coefficient Q 2 = 0.739. Predictive ability of the selected model was also confirmed by the leave one out cross validation method and by leave 33 % out Q 2 = 0.688. The QSAR model indicates that the descriptors (logP, SI3, LM, and DVZ) play an important role in the CRTh2 receptor antagonist activities. Results of the present study may be useful in the designing of more potent 2,4-disubstituted phenoxyacetic acid derivatives as CRTh2 receptor antagonist agents.

Difference in the kinetics of chemiluminescence (CL) and differential scanning calorimetry records for decomposition of originally solid benzoyl peroxide continuing as a melt reaction was outlined. While the main portion of heat measured by DSC is released in the spontaneous decomposition of benzoyl peroxide starting as a homolytic scission of peroxidic bonds, the CL light emission in oxygen comes presumably from the subsequent disproportionation reaction of polyphenyl peroxyl radicals and monitors the induced decomposition of peroxide. Thermogravimetry revealed that oxygen remains partially bound to the products of benzoyl peroxide decomposition.

Plasma-polymerized films of vinyltriethoxysilane were surface characterized using the sessile drop technique. The surface free energy and its components were evaluated using the Owens-Wendt-Kaelble geometric mean method, Wu harmonic mean method, and van Oss, Chaudhury, and Good acid-base theory. Influence of deposition conditions on the surface free energy was demonstrated in the study. Improved wettability of the films was related to the diminished concentration of apolar methyl groups in plasma polymers. An increased concentration of carbonyl and hydroxyl groups resulted in a very small improvement of the polar component.

A simple, rapid, and highly sensitive spectrofluorimetric method for the determination of acitretin was developed based on the strong green fluorescence of acitretin. Influence of organic solvents on the fluorescence spectra of acitretin was studied. Effects of pH, standing time, and foreign ions on the determination of acitretin were also examined. Under the optimum conditions, linear relationship between the relative fluorescence intensity and the concentration of acitretin in the range of 30.0–1100 ng mL−1 was obtained. Detection limit of this method is 9.56 ng mL−1 for acitretin. Relative standard deviation for the determination of 480 ng mL−1 of acitretin was 1.70 %. This method was used for the determination of acitretin in pharmaceuticals and the results were compared with those obtained by the HPLC method.

Fatty acid profile data for refined cold-pressed Trichosanthes kirilowii Maxim. seed oil, in comparison to other commercially available oils — olive, rapeseed and camellia, are presented. Trichosanthes kirilowii Maxim. seed oil has high oleic and linoleic acid content and high polyunsaturated acid content. Squalene elutes as a distinct peak in the GC chromatograph. For a positive identification, MS detection was used. In the samples analyzed, squalene occurred in the range of 57.4–68.2 mg g−1.

Areas of fusion and crystallization peaks of K3TaO2F4 and KTaF6 were measured using the DSC mode of a high-temperature calorimeter (SETARAM 1800 K). On the basis of these quantities, considering the temperature dependence of the calorimeter sensitivity, values of the fusion enthalpy of K3TaO2F4 at the fusion temperature of 1181 K of (43 ± 4) kJ mol−1 and of KTaF6 at the fusion temperature of 760 K of (8 ± 1) kJ mol−1 were determined.