Stabilisation of reactive intermediates in molecular sieves

This paper presents studies on paramagnetic intermediates, free atoms and radicals produced in γ-irradiated molecular sieves and their reactions with adsorbate molecules or exchangeable cations. Four different systems have been investigated using EPR spectroscopy, Na-A/CH₄, AgNa-A/CH₃OH, Ag-SAPO-11/C₂H₄ and AgCs-rho/NH₃. It was found that methyl radicals are formed in two different sites in Na-A/CH₄ and in one of them they are stable at room temperature. The formation of Ag·CH₂OH⁺ radical cation with one-electron bond between silver and carbon has been established in AgNa-A/CH₃OH by EPR experiments with [¹³C]CH₃OH and DFT calculations. In Ag-SAPO-11/C₂H₄ the stabilisation of biligand silver/ethylene complex, Ag⁰(C₂H₄)₂ was postulated based on EPR and DFT results. Tetrameric silver clusters (Ag ₄ ³⁺ ) produced radiolytically in AgCs-rho/NH₃ strongly interact with two ammonia molecules as was deduced from the changes in superhyperfine structure of high-field EPR line of Ag ₄ ³⁺ pentet for zeolite exposed to [¹⁴N]NH₃ and [¹⁵N]NH₃. The presented examples clearly show that the combination of radiation methods with EPR technique is very useful to study the structure and reactivity of paramagnetic intermediates.     

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.