Quantification of endocrine disruptors and pesticides in water by gas chromatography–tandem mass spectrometry. Method validation using weighted linear regression schemes

A multi-residue methodology based on a solid phase extraction followed by gas chromatography–tandem mass spectrometry was developed for trace analysis of 32 compounds in water matrices, including estrogens and several pesticides from different chemical families, some of them with endocrine disrupting properties. Matrix standard calibration solutions were prepared by adding known amounts of the analytes to a residue-free sample to compensate matrix-induced chromatographic response enhancement observed for certain pesticides. Validation was done mainly according to the International Conference on Harmonisation recommendations, as well as some European and American validation guidelines with specifications for pesticides analysis and/or GC–MS methodology. As the assumption of homoscedasticity was not met for analytical data, weighted least squares linear regression procedure was applied as a simple and effective way to counteract the greater influence of the greater concentrations on the fitted regression line, improving accuracy at the lower end of the calibration curve. The method was considered validated for 31 compounds after consistent evaluation of the key analytical parameters: specificity, linearity, limit of detection and quantification, range, precision, accuracy, extraction efficiency, stability and robustness.     

Electronegativity scheme for reactions involving radical addition to vinyl monomers

The concept of the apparent electronegativity of a reaction site has been introduced. This has been used to develop a new scheme for calculating the relative rate constants of addition of radicals with different structures to vinyl monomers. The parameters of the scheme are given for 40 reagents. The results of a comparison of calculated and literature rate constants of addition are presented.Institute of Nonaqueous Solution Chemistry, Russian Academy of Sciences, 150003 Ivanovo. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2238–2245, October, 1992.     

On obtaining localized bonding schemes from delocalized molecular-orbital wave functions

A straightforward procedure is proposed for expanding a molecular orbital determinantal wave function into a set of determinantal wave functions composed of atomic orbitals localized at the atoms of a molecule. By employing this method, atomic orbital determinants and their weights can be derived for a molecule from the computed molecular-orbital wave function. The procedure permits the interpretation of a molecular orbital determinantal wave function in terms of bonding schemes related to the classic resonance structures used by organic chemists. By using the unrestricted molecular orbital determinant, bonding schemes and their weights are obtained for butadiene, the butadiene radical cation and the acrylonitrile radical anion. Their dominant bonding schemes are in accord with the relevant resonance structures for these molecules. For the butadiene radical cation and the acrylonitrile anion they are shown to be compatible with the accepted mechanisms of the electrochemical coupling reactions of butadiene and acrylonitrile. Received: 7 August 1996 / Accepted: 18 March 1997     

Improvement of multistep WENO scheme and its extension to higher orders of accuracy

This paper presents an efficient procedure for overcoming the deficiency of weighted essentially non‐oscillatory schemes near discontinuities. Through a thorough incorporation of smoothness indicators into the weights definition, up to ninth‐order accurate multistep methods are devised, providing weighted essentially non‐oscillatory schemes with enhanced order of convergence at transition points from smooth regions to a discontinuity, while maintaining stability and the essentially non‐oscillatory behavior. We also provide a detailed analysis of the resolution power and show that the solution enhancements of the new method at smooth regions come from their ability to render smoothness indicators closer to uniformity. The new scheme exhibits similar fidelity as other multistep schemes; however, with superior characteristics in terms of robustness and efficiency, as no logical statements or mapping function is needed. Extensions to higher orders of accuracy present no extra complexity. Numerical solutions of linear advection problems and nonlinear hyperbolic conservation laws are used to demonstrate the scheme's improved behavior for shock‐capturing problems. Copyright © 2016 John Wiley & Sons, Ltd.     

A high-order finite volume method for systems of conservation laws—Multi-dimensional Optimal Order Detection (MOOD)

In this paper, we investigate an original way to deal with the problems generated by the limitation process of high-order finite volume methods based on polynomial reconstructions. Multi-dimensional Optimal Order Detection (MOOD) breaks away from classical limitations employed in high-order methods. The proposed method consists of detecting problematic situations after each time update of the solution and of reducing the local polynomial degree before recomputing the solution. As multi-dimensional MUSCL methods, the concept is simple and independent of mesh structure. Moreover MOOD is able to take physical constraints such as density and pressure positivity into account through an “a posteriori” detection. Numerical results on classical and demanding test cases for advection and Euler system are presented on quadrangular meshes to support the promising potential of this approach.     

High-order accurate dissipative weighted compact nonlinear schemes

Based on the method deriving dissipative compact linear schemes (DCS), novel high-order dissipative weighted compact nonlinear schemes (DWCNS) are developed. By Fourier analysis,the dissipative and dispersive features of DWCNS are discussed. In view of the modified wave number, the DWCNS are equivalent to the fifth-order upwind biased explicit schemes in smooth regions and the interpolations at cell-edges dominate the accuracy of DWCNS. Boundary and near boundary schemes are developed and the asymptotic stabilities of DWCNS on both uniform and stretching grids are analyzed. The multi-dimensional implementations for Euler and Navier-Stokes equations are discussed. Several numerical inviscid and viscous results are given which show the good performances of the DWCNS for discontinuities capturing, high accuracy for boundary layer resolutions, good convergent rates (the root-mean-square of residuals approaching machine zero for solutions with strong shocks) and especially the damping effect on the spudous oscillations which were found in the solutions obtained by TVD and ENO schemes.     

Indexes and Special Discretization Methods for Linear partial Differential Algebraic Equations

Linear partial differential algebraic equations (PDAEs) of the form Au _t(t, x) + Bu _xx(t, x) + Cu(t, x) = f(t, x) are studied where at least one of the matrices A, B R ^n×n is singular. For these systems we introduce a uniform differential time index and a differential space index. We show that in contrast to problems with regular matrices A and B the initial conditions and/or boundary conditions for problems with singular matrices A and B have to fulfill certain consistency conditions. Furthermore, two numerical methods for solving PDAEs are considered. In two theorems it is shown that there is a strong dependence of the order of convergence on these indexes. We present examples for the calculation of the order of convergence and give results of numerical calculations for several aspects encountered in the numerical solution of PDAEs.     

Non-expansive Mappings and Iterative Methods in Uniformly Convex Banach Spaces

In this article, we will investigate the properties of iterative sequence for non-expansive mappings and present several strong and weak convergence results of successive approximations to fixed points of non-expansive mappings in uniformly convex Banach spaces. The results presented in this article generalize and improve various ones concerned with constructive techniques for the fixed points of non-expansive mappings.     

High order accurate,one-sided finite-difference approximations to concentration gradients at the boundaries,for the simulation of electrochemical reaction-diffusion problems in one-dimensional space geometry

Accurate calculation of concentration gradients at the boundaries is crucial in electrochemical kinetic simulations, owing to the frequent occurrence of gradient-dependent boundary conditions, and the importance of the gradient-dependent electric current. By using the information about higher spatial derivatives of the concentrations, contained in the time-dependent, kinetic reaction-diffusion partial differential equation(s) in one-dimensional space geometry, under appropriate assumptions it is possible to increase the accuracy orders of the conventional, one-sided n-point finite-difference formulae for the concentration gradients at the boundaries, without increasing n. In this way a new class of high order accurate gradient approximations is derived, and tested in simulations of potential-step chronoamperometric and current-step chronopotentiometric transients for the Reinert-Berg system. The new formulae possess advantages over the conventional gradient approximations. For example, they allow one to obtain a third order accuracy by using two space points only, or fourth order accuracy by using three points, and yet they yield smaller errors than the conventional four-point, or five-point formulae, respectively. Needing fewer points, for approximating the gradients with a given accuracy, simplifies also the solution of the linear algebraic equations arising from the application of implicit time integration schemes.     

Hilbert schemes, polygraphs and the Macdonald positivity conjecture

We study the isospectral Hilbert scheme , defined as the reduced fiber product of with the Hilbert scheme of points in the plane , over the symmetric power . By a theorem of Fogarty, is smooth. We prove that is normal, Cohen-Macaulay and Gorenstein, and hence flat over . We derive two important consequences.

(1) We prove the strong form of the conjecture of Garsia and the author, giving a representation-theoretic interpretation of the Kostka-Macdonald coefficients . This establishes the Macdonald positivity conjecture, namely that .

(2) We show that the Hilbert scheme is isomorphic to the -Hilbert scheme of Nakamura, in such a way that is identified with the universal family over . From this point of view, describes the fiber of a character sheaf at a torus-fixed point of corresponding to .

The proofs rely on a study of certain subspace arrangements , called polygraphs, whose coordinate rings carry geometric information about . The key result is that is a free module over the polynomial ring in one set of coordinates on . This is proven by an intricate inductive argument based on elementary commutative algebra.