A silver nanoparticle-based method for determination of antioxidant capacity of rapeseed and its products

A novel silver nanoparticle-based (AgNP) method and two modified procedures, ferric reducing antioxidant power (FRAP) and 2,2'-diphenyl-1-picrylhydrazyl (DPPH), were used for determination of antioxidant capacities of the ethanolic, methanolic, methanolic-aqueous (1?:?1 v/v) and aqueous extracts of rapeseed and its products. The AgNP method based on the electron-transfer reaction between silver ions and antioxidants in an optimized ammonium buffer medium (pH = 8.4) and determination of silver nanoparticle formation has been elaborated. The novel AgNP method was validated using sinapic acid, gallic acid, caffeic acid, ascorbic acid and quercetin as standard antioxidant solutions in concentration ranges of 0.03-0.21 μmol mL(-1), 0.02-0.20 μmol mL(-1), 0.01-0.18 μmol mL(-1), 0.03-0.30 μmol mL(-1) and 0.001-0.009 μmol mL(-1). The calculated detection (DL = 0.01, 0.02, 0.009, 0.02 and 0.0004 μmol mL(-1) for sinapic, gallic, caffeic, ascorbic acids and quercetin, respectively) and quantification limits (QL = 0.04, 0.06, 0.03, 0.08 and 0.001 μmol mL(-1) for sinapic, gallic, caffeic, ascorbic acids and quercetin, respectively) confirm linearity concentration ranges for determination of antioxidant capacity by AgNP assay. The average antioxidant capacities of the studied rapeseed samples ranged between 14.7 and 126.2 μmol sinapic acid per gram for the proposed AgNP method, 7.4-112.7 μmol sinapic acid per gram for the FRAP method and 39.1-339.8 μmol sinapic acid per gram for DPPH assay. The methanol-water mixture (1:1 v/v) was the most efficient solvent for extraction of antioxidants from the studied rapeseed samples. There are significant, positive correlations between the novel AgNP and the modified FRAP, DPPH and FC methods for all extracts of the studied rapeseed samples (r = 0.7564-0.8516, p < 0.001). Satisfactory values of precision (RSD = 1.2-4.4%) and accuracy (recovery = 95.6-104.6%, except methanolic extracts) demonstrate the benefit of the proposed AgNP method for analysis of the antioxidant capacity of rapeseed samples. Results of the principal component analysis (PCA) indicate that there are differences between the total amounts of antioxidants in rapeseed samples extracted by different solvents.     

Poly(vinyl alcohol)-based Amphiphilic Copolymer Aggregates as Drug Carrying Nanoparticles

A series of amphiphilic polyisobutylene-block-poly(vinyl alcohol) (PIB-b-PVA) copolymers of constant PIB and varying PVA block length was synthesized by living carbocationic polymerization and their solution behavior was studied. The synthesis involved the preparation of polyisobutylene-b-poly(tert.-butyl vinyl ether) followed by hydrolysis with hydrogen bromide. The copolymers were characterized by gel permeation chromatography, ¹H-NMR, and MALDI-TOF MS methods. The micellization behavior of the copolymers was investigated in aqueous media by direct dissolution and dialysis using static and dynamic light scattering. The critical micelle concentration, micelle size, aggregation number, and micelle shape were determined. The ability of the aggregates as drug carrying nanodevices was also investigated by doping them with indomethacin. UV-Vis measurements showed that the solubility of indomethacine increased significantly. Our findings suggest that the solubility is largely dependent upon the block segment ratios.     

Study of the influence of physical aging on macroradical decay in poly(methyl methacrylate)

The macroradical decay in poly(methyl methacrylate) samples with different thermal histories was investigated in the temperature interval 20–100 °C using ESR spectroscopy and the second order kinetic model. The rate constants exhibit two different regimes with the transitions atT _tr=68±1°C which are independent of thermal treatment. ForT<T _tr andT>T _tr the rate constants as well as the corresponding activation parameters are sensitive to history because of different physical microstructures. The compensation law, i.e., the linear relation between lnk _{o, eff} andE _eff, was analyzed in terms of the so-called compensation quantitiesk _c andT _c and a proximity betweenT _c=T _tr andT _o=53±3 °C — Vogel temperature for -segmental dynamics was found. A comparison of kinetic and dynamic data suggests that the decay of terminal macroradicals in the low-temperature region is controlled by secondary relaxations and that the -mobility contributes to a more rapid decay at higher temperatures belowT _g.     

Lipophilicity determination of some new crown ethers by reversed-phase thin-layer chromatography

Summary The lipophilicity of 28 modified crown ether derivatives was determined by reversed-phase thin-layer chromatography (RPTLC) using various organic phases and supports. The lipophilicity values determined in different RPTLC systems showed good correlations, however the quality of the organic phase (methanol, acetone, acetonitrile) and the support characteristics influenced to a small extent the determination.     

EPR study of free radicals in a main chain thermotropic polymer

Free radicals were generated in a rigid rod-like copolymer via mechanical route and by gamma radiation. The (EPR) method was used for studying free radicals formed at 123 K. The spectra of free radicals observed and the influence of molecular motions on the transport of radical centers in the fracture surface layer are discussed.     

Comparative bioanalytical study of3H-deramciclane in dog plasma, using a gas chromatography-nitrogen-selective detection (GC-NPD), a new GC-radiochemical detection (GC-RD) and a liquid scintillation method

Summary A new, highly sensitive and selective gas chromatography method, using radiochemical detection (GC-DR) was developed for the selective determination of³H-labelled deramciclane and its N-desmethyl metabolite in dog plasma. Inter-day accuracy and precision, as well as system suitability of the GC-RD method was investigated during the method validation. The calibration curve was proved to be linear (r=0.9986) in a wide concentration range (13–1000 ngeqv mL⁻¹) The lower limit of quantitation (LLOQ) was 13.7 ngeqv mL⁻¹, and the limit of the detection (LOD) was 1 ngeqv mL⁻¹. Using this new GC-RD method, plasma levels of³H-labelled deramciclane and its metabolite were determined in dogs, after the administration of a single 10 mg kg⁻¹ oral dose. Pharmacokinetic curves and the calculated pharmacokinetic parameters were compared to those obtained using a previously elaborated gas chromatography-nitrogen selective detection method (GC-NPD) and to those obtained by measuring the plasma level of total radioactivity (liquid scintillation counting, LSC). Pharmacokinetic curves and the calculated pharmacokinetic parameters obtained with the two different gas chromatography detection methods (NPD and RD) showed good correlation. Comparison of these results to those acquired by total radioactivity measurement demonstrated that deramciclane was intensively metabolised. Moreover, the biological half-life (t ₁ ^2/β ) of the unknown metabolites proved to be more than a magnitude longer than the half-life of the parent compound or that of N-desmethyl metabolite. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997.     

Kinetic Modeling of the Decomposition of Carbon Tetrachloride in Thermal Plasma

Decomposition of carbon tetrachloride in a RF thermal plasma reactor was investigated in argon atmosphere. The net conversion of CCl₄ and the main products of its decomposition were determined from the mass spectrometric analysis of outlet gases. Flow and temperature profiles in the reactor were calculated and concentration profiles of the species along the axis of the reactor were estimated using a newly developed chemical kinetic mechanism, containing 12 species and 34 reaction steps. The simulations indicated that all carbon tetrachloride decomposed within a few microseconds. However, CCl₄ was partly recombined from its decomposition products. The calculations predicted 70\% net conversion of CCl₄, which was close to the experimentally determined value of 60\%. A thermodynamic equilibrium model also simulated the decomposition. Results of the kinetic and thermodynamic simulations agreed well above 2000 K. However, below 2000 K the thermodynamic equilibrium model gave wrong predictions. Therefore, application of detailed kinetic mechanisms is recommended for modeling CCl₄ decomposition under thermal plasma conditions.     

Monitoring of optical isomers of chiral alcohols and derivatives by chiral gas chromatography. Effect of derivatization on the enantio-differentiation

Summary Gas chromatographic chiral separation of several chiral 2-and 3-alkanols and diols was studied both in their free hydroxyl and in their trimethylsilyl ether forms. First, the derivatization procedure was verified through the identification of the trimethylsilyl ethers formed on the basis of their mass spectra and optimized to obtain quantitative reaction. The optimized procedure was applied to the trimethylsilylation of racemic mixtures of various hydroxyl compounds. The silylation was found to be highly effective in the improvement of the separation of the individual enantiomers. The major advantages of the derivatization process can be summarized as: (i) excellent baseline separation of the enantiomers of the silyl ethers was achieved in contrast to the parent OH-containing compounds, (ii) the sensitivity of detection highly increased, (iii) the separations do not show any significant concentration dependence and finally (iv) the analysis time needed decreased significantly. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997     

An enzyme-immunoassay for the detection of the mycotoxin zearalenone by use of yolk antibodies

The development of an enzyme-immunoassay (ELISA) for the detection of the Fusarium mycotoxin zearalenone (ZON) is described. In contrast to the common antibody isolation from mammal serum, chicken were immunized in order to isolate specific antibodies from the egg yolk. Five weeks after the start of the immunization a titer of 1:76 000 resulted from three injections without any adverse effects for the animals. Utilizing the indirect competitive assay format ZON could be detected in a concentration range between 10 and 200 μg/L. Received: 3 January 1998 / Revised: 16 March 1998 / Accepted: 20 March 1998     

Isomerization of substituted tricyclic 4,5-dihydropyrazoles

Summary The acid and base catalyzed isomerization of some tricyclic 2-pyrazolines with N-Carbamoyl-,N-thiocarbamoyl-and N-phenyl substituents was investigated. Starting fromcis ortrans 3-H, 3a-H diastereomers, equilibrium mixtures ofcis andtrans diastereomers were prepared which were separated and subsequently studied by¹H NMR and¹³C NMR spectroscopy. A mechanism for the isomerization of the pyrazolines is suggested, supported by a deuterium exchange at C-3a.

---

Isomerisierung von einigen substituierten 4,5-Dihydropyrazolen

Zusammenfassung Die Isomerisierung einiger tricyclischer 2-Pyrazoline mit N-Carbamoyl-, N-Thiocarbamoyl-und N-Phenyl-substituenten unter saurer und basischer Katalyse wurde untersucht. Ausgehend von dencis odertrans 3-H,3a-H-Diastereomeren wurdencis- undtrans Gleichgewichtsgemische gewonnen, die getrennt und durch¹H- und¹³C-NMR-Spektroskopie untersucht wurden. Ein Mechanismus für die Isomerisierung von Pyrazolinen wird vorgeschlagen, der durch den Deuteriumaustausch in Position 3a-C unterstützt wird.