Possibilities and limitations of fast GC with narrow-bore columns

In this work, two narrow-bore capillary columns with different internal diameters (I.D.) 0.15 mm (15 m length, 0.15 microm film thickness) and 0.10 mm (10 m length, 0.10 microm film thickness) with the same stationary phase (5% diphenyl 95% dimethylsiloxane), phase ratio and separation power were compared with regard to their advantages, practical limitations and applicability in fast GC on commercially available instrumentation. The column comparison concerns fast GC method development, speed and separation efficiency, the sample transfer into the column utilizing split and splitless inlet, sample capacity, detection (analysing compounds of a wide range of polarities and volatilities--even n-alkanes C16-C28 and selected pesticides) and ruggedness (in the field of ultratrace analysis of pesticide residues in real matrix). Under conditions corresponding to speed/separation efficiency trade-off 0.10 mm I.D. versus 0.15 mm I.D. column provides a speed gain of 1.74, but all other parameters investigated were better for the 0.15 mm I.D. column concerning more efficient sample transfer from inlet to the column using splitless injection, no discrimination with split injection. Better sample capacity (three times higher for the 0.15 mm than for the 0.10 mm I.D. column) resulted in improved ruggedness and simpler fast GC-MS method development.     

Sample preparation methods in the analysis of pesticide residues in baby food with subsequent chromatographic determination

Pesticides are widely utilized at various stages of cultivation and during postharvest storage to protect plants against a range of pests and/or to provide quality preservation. Reliable confirmatory methods are required to monitor pesticide residues in baby foods and to ensure the safety of baby food supply. This review covers methods in which pesticide residues have been determined in baby food by the use of a wide range of chromatographic techniques after various sample preparation steps. The main attention is paid to the evaluation and improvement of sample extraction and clean-up methods (liquid extraction, solid-phase extraction (SPE), dispersive SPE (DSPE), microextraction procedures, matrix solid-phase dispersion (MSPD) and supercritical fluid extraction (SFE)) considering low concentration levels of pesticide residues in baby food resulting from stringent European Union (EU) legislation. Instrumental aspects together with the matrix effects significantly contributing to the most important parameters considered in pesticide residues analysis of baby food--limits of detection (LODs) and limits of quantification (LOQs) were included within the scope of this overview. Paper involves also monitoring studies.     

Comparison of isothermal and non-isothermal chemiluminescence and differential scanning calorimetry experiments with benzoyl peroxide

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.     

Exchange dipole interaction in a multilevel cooperative system of atoms

Atomic systems with three or more equidistant energy levels, in which a cascade process is possible, are considered. Hamiltonians obtained for such systems are analogous to Heisenberg Hamiltonians, but for systems with integral spins. For Dicke states in multilevel systems, quantum-mechanical mean values of the energy of a cooperative system are calculated taking into account weak interactions between atoms. The type of emission preceding superradiant avalanche emission of the system is analyzed. It can be expected that a coherent state may be formed, in which collective processes affect one another not only via population of the intermediate common layer, but also via phasing of pure quantum states. The single superfluorescence pulse that can be formed in this case is not a simple superposition of two or more pulses of sequential superradiant transitions in two-level systems.     

A method for determining errors of a static fiber-optic gyrocompass

The influence of intrinsic noise and signal drift on the accuracy of a static fiber-optic gyrocompass (FOG) is analyzed theoretically, and a method is proposed to determine the errors of the gyrocompass experimentally. From this it is possible to choose an optimum algorithm for measuring the FOG signal and calculating the direction angle with respect to north. Real measurements of the accuracy of an operating gyrocompass yield errors of order 1° (rms). Zh. Tekh. Fiz. 67, 110–113 (September 1997)     

Exchange self-polarization of an electron beam

Self-organization of a beam of free electrons injected by an optical cathode is discussed. It is shown that exchange interaction may cause beam self-polarization in a vacuum and sustain beam polarization in the material.     

Thermo-oxidation of polypropylene in the presence of PbO

A significant retardation effect by PbO on the formation of volatile products from isotactic polypropylene (IPP) was found at temperatures up to 380°C. The effect is explained by the formation of a surface active form of PbO (possibly Pb₃O₄) which is formed by interaction of PbO with peroxy radicals. Primary and secondary alkyl radicals terminate effectively on the active surface and the kinetic length of the degradation reaction is thus decreased.A compensation effect exists between the Arrhenius parameters ln A and E for both inhibited and uninhibited formation of volatile products.     

Survey of low-level endocrine disrupting pesticides in food matrices in Slovakia

The search on endocrine disrupting chemicals (EDCs) in non-fatty food was evaluated. A fast, high-throughput, accurate, multiresidue method for the analysis of selected EDC pesticides in fruit and vegetable food samples was developed. The QuEChERS technique was used for sample preparation. Fast GC-MS was performed with a narrow-bore capillary column and a quadrupole benchtop detector with electron ionization (EI) and negative chemical ionization (NCI). A part of the work was devoted to the comparison of NCI versus EI approach concerning the sensitivity of detection and to the study of selectivity enhancement in NCI mode. Matrix-matched standard solutions were utilized for calibration. The methods validation was performed. Fortification studies at 1, 5, 10 and 250?µg?kg^?1 for 35 pesticides in EI mode and 0.1, 1, 5 and 250?µg?kg^?1 for 28 pesticides in NCI mode were performed. Average recoveries for each fortification level ranged from 70 to 110% with >80% of recoveries between 90 and 110%. Limits of quantification (LOQs) were established at 5?µg?kg^?1 for EI and at 1?µg?kg^?1 for NCI mode, which is lower than the lowest maximum residue level (MRL) value set by the European Commission in fruit and vegetables. The developed and validated fast GC-MS method was successfully applied to the search of EDC pesticides at ultratrace concentration level in real fruit and vegetable samples in Slovakia. Thirty-four samples of 20 different commodities were analyzed. Seven samples contained residues of three or more EDCs pesticides.     

Inhibited Oxidation of Cumene and Polymerization of Styrene Investigated by Solution Microcalorimetry

The application of solution microcalorimetry was demonstrated on two model examples – inhibited oxidation of cumene and radical polymerization of styrene.From the experimental dependences of the rate of heat release on time, the rate constants k ₇ of the interaction of an inhibitor with radicals of substrate (RO ₂ ^. or R^.) in oxidation or in polymerization were determined for the set of inhibitors of N-aryl N-(2-quinone) amine series. It was shown that these compounds are weak inhibitors of oxidation of cumene and rather efficient inhibitor of polymerization of styrene.This revised version was published online in November 2005 with corrections to the Cover Date.     

Coherent amplification of beams of atoms inelastically scattered by the Bose-Einstein condensate

The subject of consideration is coherent amplification of a beam of impurity atoms inelastically scattered by a system of ultracold atoms with collectively excited modes. A kinematic model of weak localization of a new type is used that provides a straightforward explanation for this phenomenon and also makes it possible to derive the angular dependences of the scattering intensity. Based on this model, angular and energy criteria for the existence of the new-type weak localization in an ultracold system of atoms (the Bose-Einstein condensate) are determined. Particular emphasis is on how the principle of indistinguishability influences the weak localization of a beam of atoms inelastically scattered by the Bose-Einstein condensate when scattered and condensed atoms are identical.