Comparison of extraction techniques for gas chromatographic determination of volatile carbonyl compounds in alcohols

Two extraction procedures, i.e. conventional liquid-liquid extraction (LLE) and liquid solid-phase microextraction (SPME) for extraction of the oximes formed after derivatization of carbonyl compounds with o-(2,3, 4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA) in alcoholic solutions have been compared. The limit of detection for LLE followed by GC-ECD determination of C₁–C₆ was in the range of 0.23–3.3 μg/L, whereas for liquid SPME 0.005–0.33 μg/L. Both methods elaborated can be applied to the determination of carbonyl compounds present in spirits and alcoholic beverages. Received: 26 September 2000 / Revised: 14 January 2001 / Accepted: 16 January 2001     

Classical Limit in Fuzzy Set Models of Spin-1/2 Quantum Logics

The classical limit of fuzzy set models ofspin-1/2 quantum logics is obtained in the course of adefuzzyfication procedure. The conditionsunder which the limiting structure is a Boolean algebra are studied.     

GRID formalism for the comparative molecular surface analysis: application to the CoMFA benchmark steroids, azo dyes, and HEPT derivatives

Shape analysis is a powerful tool in chemistry and drug design, and molecular surface defines shape in the molecular scale. In the current publication we presented a novel formalism for the comparative molecular surface analysis (s-CoMSA). The method enables both quantitative modeling of 3D-QSAR and finding possible pharmacophoric sites. The method provides very predictive models for the CBG activity of the benchmark steroid series, tinctorial properties of the heterocyclic azo dyes and anti-HIV activity of the HEPT series.     

Simultaneous photolysis of directly linked porphyrin-diazonium salt molecule

Meso-tetra-(p-diazoniumphenyl) porphyrin (TDSPP) can be photolyzed only under anaerobic conditions with a yield of 0.18 during simultaneous irradiation with He-Ne laser light (632.8 nm) and light of the 313 nm line of 0 mercury lamp. The excited singlet state of TDSPP is quenched by externalp-methoxybenzene diazoniumtetra fluoroborate (MeODS) with a rate constant of 9.7 × 10⁹M⁻¹s⁻¹. TDSPP and MeODS interact in the ground state with an equilibrium constant of about 16M⁻¹ and form a fluorescent but photochemically inactive.     

Mesoionic compounds — structure and NMR parameters

It has been shown that¹H,¹³C,¹⁴N,¹⁵N,¹⁷O, and⁷⁷Se NMR are very successful techniques for the identification and investigation of potential valence tautomerism in all types of mesoionic compounds. Especially the combined use of¹⁴N and¹⁵N NMR studies has been shown to be very effective in solving structural problems. From¹⁵N NMR it is possible to obtain accurate chemical shifts and spin-spin couplings, whereas the¹⁴N NMR spectra provide us with nuclear relaxation and some chemical shift data. In particular¹⁴N NMR is very useful for the identification of charged nitrogen atoms in molecules containing non equivalent nitrogen positions. This information is available from the relative¹⁴N signal widths, which depend upon the rates of¹⁴N relaxation, positively charged nitrogen atoms usually have relatively slow¹⁴N relaxation rates thus giving rather sharp NMR signals. Some solid state, CP MAS,¹³C and¹⁵N NMR results are available for comparison with the solution NMR data.Published in Khimiya Geterotsiklischeskikh Soedinenii, No. 9, pp. 1180–1199. September 1995.     

Multilayer adsorption from multicomponent liquid mixtures on solid surfaces

Multilayer adsorption of multicomponent liquid mixtures on homogeneous and heterogeneous solid surfaces is discussed. Heterogeneity effects of the adsorbent surface have been taken into account in calculation of mole fractions of the components in the first adsorbed layer. The model calculations, illustrating multilayer and heterogeneity effects, have been performed for adsorption of ternary liquid mixtures.

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Mehrschicht-Adsorption von flüssigen Mehrkomponentenmischungen auf festen Oberflächen

Zusammenfassung Es wird die Mehrschichtadsorption auf homogenen und heterogenen Oberflächen diskutiert. Bei der Berechnung der Molbrüche der Komponenten der ersten adsorbierten Schicht wurden Heterogenitäts-Effekte berücksichtigt. Die Modellrechnungen wurden an ternären flüssigen Mischungen vorgenommen.

     

Cocyclic subshifts

Motivated by the computations in the theory of cohomological Conley index, cocyclic subshifts are the supports of locally constant matrix cocycles on the full shift over a finite alphabet. They properly generalize sofic systems and topological Markov chains; and, via the Wedderburn-Artin theory of finite-dimensional algebras, admit a similar structure theory with a spectral decomposition into mixing components. These components have specification, which implies intrinsic ergodicity and entropy generation by sequences of horseshoes. Also, a zeta-like generating function for cocyclic subshifts leads to simple criteria for existence of a factor map onto the full two-shift – which gives practical tools for detecting chaos in general discrete dynamical systems. Received June 30, 1997; in final form May 21, 1999     

Mechanism of Catalyst Action in Interfacial Polycondensation of Chlorobisphenol and Isophthaloyl Chloride

The mechanism of action of quaternary ammonium salt catalysts in the synthesis of aromatic polyesters was investigated. The possibility of formation of compounds of these salts and bisphenols and their extraction in the form of an ion pair into the organic phase was investigated. The structure of the compounds obtained was determined.     

Suppression of heating rates in cryogenic surface-electrode ion traps

Dense arrays of trapped ions provide one way of scaling up ion trap quantum information processing. However, miniaturization of ion traps is currently limited by sharply increasing motional state decoherence at sub-100 mum ion-electrode distances. We characterize heating rates in cryogenically cooled surface-electrode traps, with characteristic sizes in the 75 to 150 mum range. Upon cooling to 6 K, the measured rates are suppressed by 7 orders of magnitude, 2 orders of magnitude below previously published data of similarly sized traps operated at room temperature. The observed noise depends strongly on the fabrication process, which suggests further improvements are possible.     

Partitioning of atmospheric carbon dioxide over Central Europe: insights from combined measurements of CO2 mixing ratios and their carbon isotope composition

Regular measurements of atmospheric CO (2) mixing ratios and their carbon isotope composition ((13)C/(12)C and (14)C/(12)C ratios) performed between 2005 and 2009 at two sites of contrasting characteristics (Krakow and the remote mountain site Kasprowy Wierch) located in southern Poland were used to derive fossil fuel-related and biogenic contributions to the total CO (2) load measured at both sites. Carbon dioxide present in the atmosphere, not coming from fossil fuel and biogenic sources, was considered 'background' CO (2). In Krakow, the average contribution of fossil fuel CO (2) was approximately 3.4%. The biogenic component was of the same magnitude. Both components revealed a distinct seasonality, with the fossil fuel component reaching maximum values during winter months and the biogenic component shifted in phase by approximately 6 months. The partitioning of the local CO (2) budget for the Kasprowy Wierch site revealed large differences in the derived components: the fossil fuel component was approximately five times lower than that derived for Krakow, whereas the biogenic component was negative in summer, pointing to the importance of photosynthetic sink associated with extensive forests in the neighbourhood of the station. While the presented study has demonstrated the strength of combined measurements of CO (2) mixing ratios and their carbon isotope signature as efficient tools for elucidating the partitioning of local atmospheric CO (2) loads, it also showed the important role of the land cover and the presence of the soil in the footprint of the measurement location, which control the net biogenic surface CO (2) fluxes.