Cyclisation at very high temperature. Thermal transformations of N-alkyl and N,N-dialkyl cinnamic amides into pyrrolidin-2-ones under FVT conditions

Novel cyclisations of N-alkyl and N,N-dialkyl cinnamic amides to the corresponding pyrrolidin-2-ones under the conditions of flash vacuum thermolysis, are described. It was found that this reaction proceeds at 950-1000 °C affording a mixture of isomeric pyrrolidin-2-ones in various yields. Two possible mechanisms are proposed for the process.     

Uniqueness in the inverse transmission scattering problem for periodic media

We study the problem of the scattering by a periodic, penetrable medium. We present certain uniqueness results and give the integral equation formulation of the transmission problem which is of Fredholm type and provides the existence and continuous dependence result. Next we investigate the question of the uniqueness for the inverse transmission problem, i.e. we concentrate on the amount of information that is necessary to completely determine the profile and constitutive parameters of the scattering grating. Copyright © 1999 John Wiley & Sons, Ltd.     

Determination of the anomeric configuration of glycosyl esters of nucleoside pyrophosphates and polyisoprenyl phosphates by fast-atom bombardment tandem mass spectrometry

Collision-induced dissociation of the deprotonated molecules of glycosyl esters of nucleoside pyrophosphates and polyisoprenyl (dolichyl and polyprenyl) phosphates results in distinct fragmentation patterns that depend on cis-trans configuration of the phosphodiester and 2″ (or 2′, respectively)-hydroxyl groups of the glycosyl residue. At the collision-offset voltage of 0. 5 V, sugar nucleotides with cis configuration produce only one very abundant fragment of nucleoside monophosphate, whereas compounds with trans configuration give weak signals for nucleoside di- and mono-phosphates and their dehydration products. These fragmentation patterns are largely preserved at higher collision energy, with the exception that, for sugar nucleotides with trans configuration, the characteristic signals are much more abundant and a novel diagnostic fragment of [ribosyl(deoxyribosyl)-5′-P₂O₅ — H]^? is generated. In the case of polyisoprenyl-P-sugars, polyisoprenyl phosphate ion is the only fragment observed for compounds with trans configuration, whereas in compounds with cis configuration, this ion is accompanied by another abundant fragment, which is derived from the cleavage across the sugar ring and corresponds to [polyisoprenyl-PO₄-(C₂H₃O)]^?. The relative intensity ratio of the latter ion to the [polyisoprenyl-HPO₄]^? ion is close to 1 for compounds with cis configuration, but it is only about 0. 01 for compounds with trans configuration. This ratio may serve, therefore, as a diagnostic value for determination of the anomeric configuration of glycosyl esters of polyisoprenyl phosphates. It is proposed that the observed differences in fragmentation patterns of cis-trans sugar nucleotides and polyisoprenyl-P-sugars could be explained in terms of kinetic stereoelectronic effect, and a speculative mechanism of fragmentation of compounds with trans configuration is presented. For compounds with cis configuration, formation of a hydrogen bond between the C-2″(2′) hydroxyl and the phosphate group could play a crucial role in directing the specific fragmentation reactions. Consequently, the described empirical rules would hold only for compounds that have a free 2″(2′)-hydroxyl group and no alternative charge location. Owing to its simplicity, sensitivity, and tolerance of impurities, fast-atom bombardment-tandem mass spectrometry represents a suitable method for determination of the anomeric linkage of glycosyl esters of nucleoside pyrophosphates and polyisoprenyl phosphates if the absolute configuration of glycosyl residue is known and the compound fulfills the above-mentioned requirements.     

Decision Rules Derived from Optimal Decision Trees with Hypotheses

Conventional decision trees use queries each of which is based on one attribute. In this study, we also examine decision trees that handle additional queries based on hypotheses. This kind of query is similar to the equivalence queries considered in exact learning. Earlier, we designed dynamic programming algorithms for the computation of the minimum depth and the minimum number of internal nodes in decision trees that have hypotheses. Modification of these algorithms considered in the present paper permits us to build decision trees with hypotheses that are optimal relative to the depth or relative to the number of the internal nodes. We compare the length and coverage of decision rules extracted from optimal decision trees with hypotheses and decision rules extracted from optimal conventional decision trees to choose the ones that are preferable as a tool for the representation of information. To this end, we conduct computer experiments on various decision tables from the UCI Machine Learning Repository. In addition, we also consider decision tables for randomly generated Boolean functions. The collected results show that the decision rules derived from decision trees with hypotheses in many cases are better than the rules extracted from conventional decision trees.     

Qualitative and Quantitative Analysis of Secondary Metabolites in Morphological Parts of Paulownia Clon In Vitro 112® and Their Anticoagulant Properties in Whole Human Blood

It is not easy to find data in the scientific literature on the quantitative content of individual phytochemicals. It is possible to find groups of compounds and even individual compounds rather easily, but it is not known what their concentration is in cultivated or wild plants. Therefore, the subject of this study was to determine the content of individual compounds in the new Paulownia species, Oxytree, developed in a biotechnology laboratory in 2008 at La Mancha University in Spain. Six secondary metabolites were isolated, and their chemical structure was confirmed by spectral methods. An analytical method was developed, which was then used to determine the content of individual compounds in leaves, twigs, flowers and fruits of Paulownia Clon in Vitro 112^®. No flavonoids were found in twigs and fruits of Oxytree, while the highest phenylethanoid glycosides were found in twigs. In this study, we also focused on biological properties (anticoagulant or procoagulant) of extract and four fractions (A–D) of different chemical composition from Paulownia Clon in Vitro 112 leaves using whole human blood. These properties were determined based on the thrombus-formation analysis system (T-TAS), which imitates in vivo conditions to assess whole blood thrombogenecity. We observed that three fractions (A, C and D) from leaves decrease AUC₁₀ measured by T-TAS. In addition, fraction D rich in triterpenoids showed the strongest anticoagulant activity. However, in order to clarify the exact mechanism of action of the active substances present in this plant, studies closer to physiological conditions, i.e., in vivo studies, should be performed, which will also allow to determine the effects of their long-term effects.     

Evaluation of high-field asymmetric waveform ion mobility spectrometry mass spectrometry for the analysis of the mycotoxin zearalenone

A high-field asymmetric waveform ion mobility spectrometry (FAIMS)-based method for the determination of the mycotoxin zearalenone (ZON) and its metabolites α-zearalenol (α-ZOL), β-zearalenol (β-ZOL), and β-zearalanol (β-ZAL), in a cornmeal (maize) matrix is described. Detection limits achieved using the FAIMS device coupled with electrospray ionization (ESI) and mass spectrometric (MS) detection are 0.4 ng mL⁻¹ for ZON and 3 ng mL⁻¹ for α-ZOL + β-ZOL, and β-ZAL. This represents a significant improvement when compared to detection limits determined using ESI-MS or ESI-tandem mass spectrometry (MSMS) analytical methods. The developed flow-injection (FIA)-ESI-FAIMS-MS method was applied to reference materials ERM-BC-716 and ERM-BC-717 certified for ZON and excellent agreement with the certified values was observed.     

An acoustic scattering problem for periodic,inhomogeneous media

We study the problem of the scattering by a periodic, inhomogeneous, penetrable medium. Using the Dirichlet-to-Neumann operator from the classical formulation of the problem we derive a variational equation and give regularity result to show the equivalence of both formulations. We present certain uniqueness results, which by the Fredholm alternative yield existence of the solution and its continuous dependence on the incoming wave. We prove existence of a solution for special incident waves even if there is no uniqueness. A result about analytical dependence of the solution on the wave number and the incident angle is given. © 1998 B. G. Teubner Stuttgart—John Wiley & Sons, Ltd.     

Improvement of luminescent materials composed of Tb(III) ions,WO3 nanoparticles and silica xerogel as a matrix

Nanoparticles of tungsten trioxide, WO₃, are used to enhance the luminescence emission intensity of terbium(III) ions embedded in a silica matrix. Optically active components have been incorporated into silica xerogel by impregnation of silica xerogel immersed firstly in WO₃ sol and subsequently in a solution with Tb(III). Photoluminescence studies make it possible to describe a plausible mechanism of the Tb(III) enhanced luminescence that could be attributed to energy transfer via excited WO₃ nanoparticles to Tb(III) ions in the system: Tb(III) ions–WO₃ nanocrystals–SiO₂. The effect related to WO₃ nanoparticles of various sizes influences not only changes in the emission intensity and band shifting of WO₃ nanostructures but also the same spectral parameters of the emitting Tb(III) ions.     

Effects of vessel baffling on the drawdown of floating solids

The effects of baffling of an agitated vessel on the production of floating particles suspension are presented in this paper. Critical agitator speed, needed for particles dispersion in a liquid agitated in a vessel of the inner diameter of 0.295 m, was determined. The just drawdown agitator speeds were defined analogously to the Zwietering criterion. Specific agitation energy was calculated from the power consumption experimental data obtained by means of the strain gauge method. The experiments were carried out for twelve configurations of the baffles differing in number, length and their arrangement in the vessels. The following high-speed impellers were used: up- and downpumping six blade pitched blade turbines, Rushton turbine, and propeller. The impeller was located in the vessel in the height equal to two-thirds or one-third of the vessel diameter from the bottom of the vessel. The results were described in the form of a dimensionless equation. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

The process of 4‐hydroxybiphenyl synthesis from 4‐isopropylbiphenyl

The kinetics of the oxidation of 4‐isopropylbiphenyl ( 1 ) in the liquid phase by oxygen to 1‐(1,1′‐biphenyl‐4‐yl)‐1‐methylethyl hydroperoxide ( 2 ) was investigated. The oxidizability of 1 in the temperature range from 60°C to 120°C and the overall energy activation of oxidation were determined. Long‐term oxidation of 1 to 2 in the temperature range of 80–120°C was investigated, and the yield and selectivity of the process were determined. Pure 2 was obtained, and its properties were defined. 4‐Hydroxybiphenyl was obtained as a result of the acidic decomposition of 2 . © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 527–532, 2008