Assessment of applicability domain for multivariate counter-propagation artificial neural network predictive models by minimum Euclidean distance space analysis: A case study

Alongside the validation, the concept of applicability domain (AD) is probably one of the most important aspects which determine the quality as well as reliability of the established quantitative structure–activity relationship (QSAR) models. To date, a variety of approaches for AD estimation have been devised which can be applied to particular type of QSAR models and their practical utilization is extensively elaborated in the literature. The present study introduces a novel, simple, and effective distance-based method for estimation of the AD in case of developed and validated predictive counter-propagation artificial neural network (CP ANN) models through a proficient exploitation of the Euclidean distance (ED) metric in the structure-representation vector space. The performance of the method was evaluated and explained in a case study by using a pre-built and validated CP ANN model for prediction of the transport activity of the transmembrane protein bilitranslocase for a diverse set of compounds. The method was tested on two more datasets in order to confirm its performance for evaluation of the applicability domain in CP ANN models. The chemical compounds determined as potential outliers, i.e., outside of the CP ANN model AD, were confirmed in a comparative AD assessment by using the leverage approach. Moreover, the method offers a graphical depiction of the AD for fast and simple determination of the extreme points.     

Antioxidative responses to seasonal changes and chemiluminescence assay of Astragalus onobrychis leaves extract

The aim of this study was to research the seasonal changes of antioxidant enzyme activity and total antioxidant capacity in leaves of Astragalus onobrychis L. subsp. chlorocarpus (Griseb.) S. Kozuharov et D.K. Pavlova. Leaves of A. onobrychis were collected during the different stages of growth and analyzed for antioxidant enzyme activity: superoxide dismutase, catalase, guaiacol peroxidase, glutathione peroxidase. Quantities of malonyldialdehyde, superoxide radicals, and hydroxyl radicals were measured as well as the content of soluble proteins. Furthermore, total antioxidant capacity was determined by the inhibition of chemiluminescence activity of blood phagocytes by leaf extracts. Stages of vegetation significantly affected the accumulation of superoxide radicals, but there were no significant differences in hydroxyl radical quantity and lipid peroxidation levels during vegetation. Soluble proteins vary greatly between different stages of growth. Seasonal changes were found to have an effect on enzymatic activities. During the spring season, guaiacol peroxidase showed the highest levels. Catalase and glutathione peroxidase increased their activities in summer, while, during the autumn season, superoxide dismutase showed maximum activity. On the basis of chemiluminescence assay, it can be concluded that leaf extract of A. onobrychis possesses a significant antioxidant capacity thus protecting plants during environmental stress.      

Performance of Au/Ti and Au/TiO2 Nanotube Array Electrodes for Borohydride Oxidation and Oxygen Reduction Reaction in Alkaline Media

Polarization curves and complex kinetics of oxygen reduction (ORR) and borohydride oxidation (BOR) reaction were evaluated at thin Au layer on Ti and TiO₂ electrodes. TiO₂ electrodes prepared included amorphous TiO₂ (AM?TiO₂) and anatase (A?TiO₂). The electrodes structure and nanotube arrays morphology were observed by XRD and SEM, respectively. All electrodes show activity for both ORR and BOR. The use of Au layer over A?TiO₂ produces the strongest synergistic effect for ORR with exchange of 3 electrons. On the other hand, the strongest effect for BOR was observed in case of Au/Ti.     

Numerical study of flow asymmetry and self-sustained jet oscillations in geometrically symmetric cavities

In this paper we present the results of numerical investigation of self-sustained oscillations of a jet confined in a symmetric cavity. This work represents an attempt to reproduce empirical observations of asymmetric flows in geometrically symmetric systems and to extend the jet flow investigations to more complex possible scenarios. A well-known example of such two-dimensional flow has been reported experimentally and reproduced numerically for simple flow [E. Schreck, M. Schaefer, Numerical study or bifurcation in three-dimensional sudden channel expansions, Comput. Fluids 29 (2000) 583–593]. It has been found that for some particular control parameter, above its critical value (bifurcation point), the jet can be deflected to either of the two sides of the cavity. In this paper we report a similar behaviour which is, however, characterized by a more complicated flow pattern. While simple flow appears only within small cavity lengths the complex flows develops with increased cavity lengths. Unlike stationary asymmetric solutions accompanied by cavity jet oscillations, as experimentally reported in e.g., [A. Maurel, P. Ern, B.J.A. Zielinska, J.E. Wesfreid, Experimental study of self-sustained oscillations in a confined jet, Phys Rev. E 54 (1996) 3643–3651], in our investigations of both simple and complex asymmetric flow we observed the slow periodical drift of the jet from one to another side of the cavity. The essential control parameters were Reynolds number Re and the ratio length to inlet width L/d. According to experiments of Maurel et al. (1996), the jet is stable and symmetric, when both L/d and Re are below certain critical values, otherwise jet oscillations appear in both experiment and our simulation (cavity oscillations regime). However, further increase of either (or both) L/d and Re leads of so called free jet type oscillations regime. This paper describes complex jet behaviour within the later oscillations regime. We believe that both simple “classical” and “our” complex stationary asymmetric solutions (as well as superimposed cavity-type and free-jet oscillations) can be explained based on physical arguments as already done in previous works. However, the origin of slow drift motion remains still to be resolved. This might be of high importance for clear distinguishing between relevant physical and numerical features in future codes developments.     

Torus maps and the problem of a one-dimensional optical resonator with a quasiperiodically moving wall

We study the problem of the asymptotic behavior of the electromagnetic field in an optical resonator one of whose walls is at rest and the other is moving quasiperiodically (with d≥2 incommensurate frequencies). We show that this problem can be reduced to a problem about the behavior of the iterates of a map of the d-dimensional torus that preserves a foliation by irrational straight lines. In particular, the Jacobian of this map has (d−1) eigenvalues equal to 1. We present rigorous and numerical results about several dynamical features of such maps. We also show how these dynamical features translate into properties for the field in the cavity. In particular, we show that when the torus map satisfies a KAM theorem—which happens for a Cantor set of positive measure of parameters—the energy of the electromagnetic field remains bounded. When the torus map is in a resonant region—which happens in open sets of parameters inside the gaps of the previous Cantor set—the energy grows exponentially.     

Origins of stereoselectivity in optically pure phenylethaniminopyridine tris-chelates M(NN')3(n+) (M = Mn, Fe, Co, Ni and Zn)

One-pot reactions of 2-pyridinecarboxaldehyde, chiral phenylethanamines and Fe(II) give single diastereomer fac diimine complexes at thermodynamic equilibrium so that no chiral separations are required (d.r. > 200 : 1). The origins of this stereoselectivity are partly steric and partly a result of the presence of three sets of inter-ligand parallel-offset π-stacking interactions. Mn(II), Co(II), Co(III), Ni(II) and Zn(II) give similar fac structures, alongside the imidazole analogues for Fe(II). While most of the complexes are paramagnetic, the series of molecular structures allows us to assess the influence of the π-stacking present, and there is a strong correlation between this and the M-N bond length. Fe(II) is close to optimal. For the larger Zn(II) ion, very weak π-stacking leads to poorer measured stereoselectivity (NMR) but this is improved with increased solvent polarity. The mechanism of stereoselection is further investigated via DFT calculations, chiroptical spectroscopy and the use of synthetic probes.     

A new potentiometric sensor for the determination of α-amylase activity

A platinum redox sensor for the direct potentiometric determination of α-amylase concentration has been described. The sensor measured the amount of triiodide released from a starch-triiodide complex, which was correlated with the α-amylase activity after biocatalytic starch degradation. The composition and stability of the potassium triiodide solution was optimized. The starch-triiodide complex was characterized potentiometrically at variable starch and triiodide concentrations. The response mechanism of the platinum redox sensor towards α-amylase was proposed and the appropriate theoretical model was elaborated. The results obtained using the redox sensor exhibited satisfactory accuracy and precision and good agreement with a standard spectrophotometric method and high-sensitive fully automated descret analyser method. The sensor was tested on pure α-amylase (EC 3.2.1.1, Fluka, Switzerland), industrial granulated α-amylase Duramyl 120 T and an industrial cogranulate of protease and α-amylase Everlase/Duramyl 8.0 T/60 T. The detection limit was found to be 1.944 mU for α-amylase in the range of 0-0.54 U (0-15 μg), 0.030 mKNU for Duramyl 120 T in the range of 0-9.6 mKNU (0-80 μg) and 0.032 mKNU for Everlase/Duramyl 8.0 T/60 T in the range of 0-9.24 mKNU (0-140 μg).     

A geometric analysis of front propagation in a family of degenerate reaction-diffusion equations with cutoff

We investigate the effects of a Heaviside cutoff on the dynamics of traveling fronts in a family of scalar reaction-diffusion equations with degenerate polynomial potential that includes the classical Zeldovich equation. We prove the existence and uniqueness of front solutions in the presence of the cutoff, and we derive the leading-order asymptotics of the corresponding propagation speed in terms of the cutoff parameter. For the Zeldovich equation, an explicit solution to the equation without cutoff is known, which allows us to calculate higher-order terms in the resulting expansion for the front speed; in particular, we prove the occurrence of logarithmic (switchback) terms in that case. Our analysis relies on geometric methods from dynamical systems theory and, in particular, on the desingularization technique known as ‘blow-up.’     

Anion-templated supramolecular C3 assembly for efficient inclusion of charge-dispersed anions into hydrogen-bonded networks

The binding properties and conformational adaptability of a known nitrate/sulfate receptor N,N'-3-azapentane-1,5-bis[3-(1-aminoethylidene)-6-methyl-3H-pyran-2,4-dione] (L) toward various charge-dispersed monoanions (HSO(3)(-), ClO(4)(-), IO(4)(-), PF(6)(-), and SbF(6)(-)) are considered. These anions template the folding of three HL(+) species through a self-assembly process into a new hollow supramolecular trication. During the self-assembly, all strong hydrogen-bond donors of the podand become coordinatively saturated by interactions with the oxo functionalities from other HL(+) molecules. In that way, only the weak hydrogen-bond-donating groups in the exterior part of the receptor are accessible for anion binding. The investigated anions are accommodated in the hydrophobic pockets of the isomorphous hydrogen-bonded frameworks, which serve as a basis for selective crystallization from the highly competitive anion/solvent systems. This behavior is discussed in terms of size and geometry of the anions as well as the receptor's coordination capabilities to provide the most favorable surroundings for guest inclusion both in solution and in the solid state.