Electron ionization mass spectral study of oxo- and thio derivatives of minor tobacco alkaloids

The electron-ionization mass spectra (EI-MS) of oxo- and thio-derivatives of minor tobacco alkaloids and structurally similar piperidine alkaloids, i.e. thiocotinine (1), 2'-oxo-N-methylanabasine (2), 2'-thio-N- methylanabasine (3), 2'-oxoanabasamine (4) and 2'-thioanabasamine (5) are discussed and general fragmentation routes of their molecular cations are proposed. Comparison of the data obtained for 1 with the EI-MS data of metameric metabolites of nicotine: 3'-hydroxycotinine, (A) and 5'-hydroxycotinine, (B) allows a differentiation between these metamers. The data will be useful for the identification of metabolites of alkaloids of these types in biological matrices.     

Imidazo[1,2-a]pyridines susceptible to excited state intramolecular proton transfer: one-pot synthesis via an Ortoleva-King reaction

A short and efficient route to a broad range of imidazo[1,2-a]pyridines from 2-aminopyridines and acetophenones is achieved by a tandem, one-pot process starting with an Ortoleva-King reaction. Optimal conditions for the first step were established after examining various reaction parameters (solvent, reagent ratios, and temperature). The conditions identified (1st step, neat, 2.3 equiv of 2-aminopyridine, 1.20 equiv of I(2), 4 h, 110 °C; 2nd step, NaOH(aq), 1 h, 100 °C) resulted in the formation of imidazo[1,2-a]pyridines in 40-60% yields. The synthesis is compatible with various functionalities (OH, NMe(2), Br, OMe). Products containing a 2-(2'-hydroxyphenyl) substituent undergo excited state intramolecular proton transfer (ESIPT) in nonpolar and polar-aprotic solvents. Although ESIPT-type emission in nonpolar solvents is weak, the Stokes shifts are very high (11000 cm(-1)). The comparison of the properties of six ESIPT-capable imidazo[1,2-a]pyridines shows the influence of various substituents on emission characteristics. All of them also display strong, solid-state emission in blue-green-yellow region. 2-Aryl-imidazo[1,2-a]pyridines not capable of ESIPT emit in the blue region, displaying high fluorescence quantum yield.     

Noise and coupling induced synchronization in a network of chaotic neurons

The synchronization in four forced FitzHugh–Nagumo (FHN) systems is studied, both experimentally and by numerical simulations of a model. We show that synchronization may be achieved either by coupling of systems through bidirectional diffusive interactions, by introducing a common noise to all systems or by combining both ingredients, noise and coupling together. Here we consider white and colored noises, showing that the colored noise is more efficient in synchronizing the systems respect to white noise. Moreover, a small addition of common noise allows the synchronization to occur at smaller values of the coupling strength. When the diffusive coupling in the absence of noise is considered, the system undergoes the transition to subthreshold oscillations, giving a spike suppression regime. We show that noise destroys the appearance of this dynamical regime induced by coupling.     

The analysis of the magnetic properties in the intermetallic YxGd1−xNi3 compounds

In the paper an influence of Gd/Y substitution on the magnetic properties and exchange interactions of the Y_xGd_1−xNi₃ (x=0.0, 0.2, 0.4, 0.6, 0.8, 1.0) polycrystalline compounds have been studied. The partial replacement of Gd by Y atoms is reflected in decreasing of the Curie temperature (T_C) as well as decreasing of effective the magnetic moment (μ_eff). It has been shown that such a behaviour strongly depends on the magnetic interactions. Exchange coupling parameters of R–R (A_RR), T–T (A_TT) and R–T (A_RT) have been evaluated from M(T) magnetization curves (2–300 K, 2 T) based on the mean field theory (MFT) calculation. The magnetocaloric effect (MCE) has been estimated from the family of magnetic isotherms. The magnetic entropy indicates relatively small change with the Gd/Y substitution. The value of ΔS_m(T,H) is higher for Gd-rich compounds and, respectively, decreases with Gd/Y substitution.     

LP and SDP branch-and-cut algorithms for the minimum graph bisection problem: a computational comparison

While semidefinite relaxations are known to deliver good approximations for combinatorial optimization problems like graph bisection, their practical scope is mostly associated with small dense instances. For large sparse instances, cutting plane techniques are considered the method of choice. These are also applicable for semidefinite relaxations via the spectral bundle method, which allows to exploit structural properties like sparsity. In order to evaluate the relative strengths of linear and semidefinite approaches for large sparse instances, we set up a common branch-and-cut framework for linear and semidefinite relaxations of the minimum graph bisection problem. It incorporates separation algorithms for valid inequalities of the bisection cut polytope described in a recent study by the authors. While the problem specific cuts help to strengthen the linear relaxation significantly, the semidefinite bound profits much more from separating the cycle inequalities of the cut polytope on a slightly enlarged support. Extensive numerical experiments show that this semidefinite branch-and-cut approach without problem specific cuts is a superior choice to the classical simplex approach exploiting bisection specific inequalities on a clear majority of our large sparse test instances from VLSI design and numerical optimization.     

Flow injection titration basing on the merging-zone technique

The proposed approach relies on titration of a sample that is gradually diluted in strictly controlled way in the flow injection system developed. On each step of sample dilution equal volumes of the sample and titrant solutions are simultaneously injected into two carrier streams and the zones are merged with each other. Then, they are mixed completely in the mixing chamber, merged with a stream of indicator and directed to a detector. It has been revealed that the method provides the results with accuracy better than ±3.3% (RE) and with mean repeatability lower than 1.0% (RSD). When the analyte concentration in a sample is too low to be determined directly, the procedure of titration with standard addition is exploited. The proposed approach has been successfully applied to the determination of total acidity in vinegars and magnesium and calcium in pharmaceutical products. The results obtained were comparable with those provided by the reference methods. The proposed procedure is characterized by low consumption of sample (usually less than 2 mL), titrant (about 3 mL) and indicator (about 0.6 mL). Average time of a single analysis is similar to time of traditional batch analysis.     

Determination of the Lipophilicity of Twenty-Seven Imidazo[2,1-c][1,2,4]triazine Derivatives with Strong Biological Activity by Reversed-Phase TLC. Comparison with Results Obtained by Use of Computational Algorithms

JPC – Journal of Planar Chromatography – Modern TLC - The lipophilicity, log P, of 27 novel imidazo[2,1-c][1,2,4]triazine derivatives with strong biological activity has been determined...     

The Use of Starch Drying Kinetics Curves for Experimental Determination of Its Specific Surface Area

The most popular method for the calculation of specific surface area is its determination from water vapour sorption isotherms. The study presented here has been designed for the purpose of optimisation and selection of the conditions of drying so as to allow the determination of specific surface area from plotted curves of the drying process. The results indicate that drying curves can be used as the basis for the determination of specific surface area, the values of which do not differ statistically significantly (α = 0.05) from those determined from isotherms of water vapour sorption (adsorption/desorption).     

Predictive Models of Phytosterol Degradation in Rapeseeds Stored in Bulk Based on Artificial Neural Networks and Response Surface Regression

The need to maintain the highest possible levels of bioactive components contained in raw materials requires the elaboration of tools supporting their processing operations, starting from the first stages of the food production chain. In this study, artificial neural networks (ANNs) and response surface regression (RSR) were used to develop models of phytosterol degradation in bulks of rapeseed stored under various temperatures and water activity conditions (T = 12–30 °C and a_w = 0.75–0.90). Among ANNs, networks based on a multilayer perceptron (MLP) and a radial basis function (RBF) were tested. The model input constituted a_w, temperature and storage time, whilst the model output was the phytosterol level in seeds. The ANN-based modeling turned out to be more effective in estimating phytosterol levels than the RSR, while MLP-ANNs proved to be more satisfactory than RBF-ANNs. The approximation quality of the ANNs models depended on the number of neurons and the type of activation functions in the hidden layer. The best model was provided by the MLP-ANN containing nine neurons in the hidden layer equipped with the logistic activation function. The model performance evaluation showed its high prediction accuracy and generalization capability (R² = 0.978; RMSE = 0.140). Its accuracy was also confirmed by the elliptical joint confidence region (EJCR) test. The results show the high usefulness of ANNs in predictive modeling of phytosterol degradation in rapeseeds. The elaborated MLP-ANN model may be used as a support tool in modern postharvest management systems.     

Structure, Conformation, and Stereodynamics of N-Nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonanes and N-Nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonan-9-ones(1)

The variable temperature (1)H, (13)C, and (19)F NMR spectra were measured for the title N-nitrosamines. The observed unusually low N-N rotation barriers (12-15 kcal/mol) result from a significant deviation of the nitrosamino system from planarity. A pyramidal character of the amino nitrogen was confirmed by the X-ray crystal structures of two compounds and by bathochromic shifts of the n-pi absorption bands in the UV spectra. The nonplanarity of the nitrosamino moiety is due to the strong pseudoallylic A((1,3)) strain caused by the steric interaction of the NNO group with the neighboring aryl substituents fixed in the equatorial positions of the bicyclic skeleton. In addition, the barriers to the C-C rotation of aryl groups were examined at temperatures lower than required to "freeze" the N-N rotation and different DeltaG() values were observed for the aryls oriented syn and anti to the nitroso oxygen.