Gas‐phase copper and silver complexes with phosphorothioate and phosphorodithioate pesticides investigated using electrospray ionization mass spectrometry

Efforts to improve agricultural productivity have led to a growing dependency on organophosphorus pesticides. Phosphorothioate and phosphorodithioate pesticides are organophosphorus pesticide subclasses with widespread application for the control of insects feeding on vegetables and fruits. However, even low doses of these pesticides can cause neurological problems in humans; thus, their determination and monitoring in agricultural foodstuffs is important for human health. Phosphorothioate and phosphorodithioate pesticides may be poorly ionized during electrospray, adversely affecting limits of detection. These pesticides can form complexes with Cu²⁺ and Ag⁺, however, potentially improving ionization. In the present work, we used electrospray ionization/mass spectrometry (ESI/MS) to study fenitrothion, parathion, diazinon, and malathion coordination complexes with silver and copper ions. Stable 1 : 1 and 1 : 2 metal/pesticide complexes were detected. Mass spectra acquired from pesticide solutions containing Ag⁺ or Cu²⁺ showed a significant increase in signal‐to‐background ratio over those acquired from solutions containing only the pesticides, with Ag⁺ improving detection more effectively than Cu²⁺. Addition of Ag⁺ to a pesticide solution improved the limit of detection by ten times. The relative affinity of each pesticide for Ag⁺ was related to complex stability, following the order diazinon > malathion > fenitrothion > parathion. The formation of Ag⁺–pesticide complexes can significantly improve the detection of phosphorothioate and phosphorodithioate pesticides using ESI/MS. The technique could potentially be used in reactive desorption electrospray ionization/mass spectrometry to detect phosphorothioate and phosphorodithioate pesticides on fruit and vegetable skins. Copyright © 2015 John Wiley & Sons, Ltd.     

Multi-scale Modeling of Vision-Guided Remodeling and Age-Dependent Growth of the Tree Shrew Sclera During Eye Development and Lens-Induced Myopia

The sclera uses unknown mechanisms to match the eye’s axial length to its optics during development, producing eyes with good focus (emmetropia). A myopic eye is too long for its own optics. We propose a multi-scale computational model to simulate eye development based on the assumption that scleral growth is controlled by genetic factors while scleral remodeling is driven by genetic factors and the eye’s refractive error. We define growth as a mechanism that changes the tissue volume and mass while remodeling involves internal micro-deformations that are volume-preserving at the macro-scale. The model was fitted against longitudinal refractive measurements in tree shrews of different ages and exposed to three different visual conditions: (i) normal development; (ii) negative lens wear to induce myopia; and (iii) recovery from myopia by removing the negative lens. The model was able to replicate the age- and vision-dependent response of the tree shrew experiments. Scleral growth ceased at younger age than scleral remodeling. The remodeling rate decreased as the eye emmetropized but increased at any age when a negative lens was put on. The predictive power of the model was investigated by calculating the susceptibility to scleral remodeling and the response to form deprivation myopia in tree shrews. Both predictions were in good agreement with experimental data that were not used to fit the model. We propose the first model that distinguishes scleral growth from remodeling. The good agreement of our results with experimental data supports the notion that scleral growth and scleral remodeling are two independently controlled mechanisms during eye development.     

Finite dynamic deformations of a hyperelastic,anisotropic, incompressible and prestressed tube. Applications to in vivo arteries

In this paper, we study the mechanical behavior of a prestressed tube subjected to finite dynamic deformations. The tube is assumed to be made of a hyperelastic, anisotropic and incompressible material. The analysis is carried out by using a Mooney–Rivlin stored energy function augmented with fiber reinforcements in four unidimensional orientations. A semi-analytical solution is proposed to study the radial dynamic mechanical response of an artery by using in vivo data. The optimal model parameters describing the mechanical characteristics of arterial wall microconstituents are obtained by minimizing the difference between computed and measured inner pressures over the cardiac cycle using a nonlinear regression. Theoretical and experimental results on rat carotid elastic arteries are compared in order to assess the validity of the approach by estimating differences of the model parameters and wall stresses with aging.     

Finite elastic deformations of transversely isotropic circular cylindrical tubes

We consider the finite radially symmetric deformation of a circular cylindrical tube of a homogeneous transversely isotropic elastic material subject to axial stretch, radial deformation and torsion, supported by axial load, internal pressure and end moment. Two different directions of transverse isotropy are considered: the radial direction and an arbitrary direction in planes normal locally to the radial direction, the only directions for which the considered deformation is admissible in general. In the absence of body forces, formulas are obtained for the internal pressure, and the resultant axial load and torsional moment on the ends of the tube in respect of a general strain-energy function. For a specific material model of transversely isotropic elasticity, and material and geometrical parameters, numerical results are used to illustrate the dependence of the pressure, (reduced) axial load and moment on the radial stretch and a measure of the torsional deformation for a fixed value of the axial stretch.     

A novel fuzzy C-means algorithm to generate diverse and desirable cluster solutions used by genetic-based clustering ensemble algorithms

One of the most significant discussions in the field of machine learning today is on the clustering ensemble. The clustering ensemble combines multiple partitions generated by different clustering algorithms into a single clustering solution. Genetic algorithms are known for their high ability to solve optimization problems, especially the problem of the clustering ensemble. To date, despite the major contributions to find consensus cluster partitions with application of genetic algorithms, there has been little discussion on population initialization through generative mechanisms in genetic-based clustering ensemble algorithms as well as the production of cluster partitions with favorable fitness values in first phase clustering ensembles. In this paper, a threshold fuzzy C-means algorithm, named TFCM, is proposed to solve the problem of diversity of clustering, one of the most common problems in clustering ensembles. Moreover, TFCM is able to increase the fitness of cluster partitions, such that it improves performance of genetic-based clustering ensemble algorithms. The fitness average of cluster partitions generated by TFCM are evaluated by three different objective functions and compared against other clustering algorithms. In this paper, a simple genetic-based clustering ensemble algorithm, named SGCE, is proposed, in which cluster partitions generated by the TFCM and other clustering algorithms are used as the initial population used by the SGCE. The performance of the SGCE is evaluated and compared based on the different initial populations used. The experimental results based on eleven real world datasets demonstrate that TFCM improves the fitness of cluster partitions and that the performance of the SGCE is enhanced using initial populations generated by the TFCM.     

Stokes flow in a junction of two-dimensional orthogonal channels

The purpose of this study is to calculate Stokes flow structures in relation to flow rate distribution in a junction of four orthogonal channels. Particular attention was paid to the existence of recirculation flow inside the channels for low Reynolds numbers. The presence of this recirculation flow may be observed, but only when the flow rate is relatively low in at least one of the branches.