Laser Mass Spectrometry of Organophosphorus Pesticides and Related Compounds

Abstract

Laser mass spectra obtained for 20 organophosphorus (OP) compounds were systematically evaluated for groups containing analogous structural features. Variations in fragmentation can be understood based on simple organic reactions. While detailed mechanistic interpretations of the laser mass spectra (LMS) were not possible, the qualitative features in the LMS obtained from five compounds, not in the original set, could be predicted based on the characteristics of the other OP compounds studied. The success of the prediction lends credence to the qualitative models developed for rationalizing the LMS. A specific feature in the LMS of aromatic thionophosphates is a thiono-thiolo rearrangement. Detailed investigation into the phenomena involved comparison of LMS obtained from aromatic thionophosphates with spectra from electron impact, chemical ionization, field desorption, and secondary ion mass spectrometry. These results led to the conclusion that the rearrangement in laser mass spectrometry must occur during volatilization while the molecule/ion is in the “cloud” present immediately above the laser impact area.     

Coating of polyamide 12 by sol–gel methodology

The combination of sol–gel methodology with rapid prototyping (RP) produces functionalized 3D structures with potential applications in various fields. However, this combination has been little explored. In this paper, we used the sol–gel method to deposit vanadium isopropoxide onto polyamide (PA12) constructed by RP and pretreated with acetic acid, to obtain a functionalized substrate with new thermal, physical, and chemical properties. Vanadium isopropoxide (one, five, or ten layers) was deposited onto the PA12 piece by dip-coating. We characterized the coated PA12 by thermal analyses, X-ray diffraction, and infrared spectroscopy, which revealed that V=O and Si–O–Si groups exist on the PA12 surface. PA12 coating with vanadium isopropoxide enhanced the decomposition temperature. Differential scanning calorimetry revealed increased fusion and decomposition enthalpy as a function of the PA12 coating. Therefore, deposition of vanadium isopropoxide onto PA12 pretreated with acetic acid improves the thermal stability of PA12 prepared by RP.     

Columnar Liquid‐Crystalline Dibenzopentacenodithiophenes by Photocyclization

The twofold glyoxylic Perkin reaction of perylene‐3,9‐diglyoxylic acid with thiophene‐diacetic acid followed by oxidative photocylization and reaction with α‐branched primary alkylamines yields columnar liquid‐crystalline diimides with two sulfur atoms in the condensed arene system. A broad temperature range of the hexagonal columnar mesophase is induced by racemic doubly branched alkyl chains. The HOMO and LUMO energy levels of these thiophene‐derived diimides qualify them as electron donors with respect to perylene diimides.     

Bifurcation phenomena in viscoelastic flows through a symmetric 1:4 expansion

In this work we present an investigation of viscoelastic flow in a planar sudden expansion with expansion ratio D/d = 4. We apply the modified FENE–CR constitutive model based on the non-linear finite extensibility dumbbells (FENE) model. The governing equations were solved using a finite volume method with the high-resolution CUBISTA scheme utilised for the discretisation of the convective terms in the stress and momentum equations. Our interest here is to investigate two-dimensional steady-state solutions where, above a critical Reynolds number, stable asymmetric flow states are known to occur. We report a systematic parametric investigation, clarifying the roles of Reynolds number (0.01 < Re < 100), Weissenberg number (0 < We < 100) and the solvent viscosity ratio (0.3 < β < 1). For most simulations the extensibility parameter of the FENE model was kept constant, at a value L² = 100, but some exploration of its effect in the range 100–500 shows a rather minor influence. The results given comprise flow patterns, streamlines and vortex sizes and intensities, and pressure and velocity distributions along the centreline (i.e. y = 0). For the Newtonian case, in agreement with previous studies, a bifurcation to asymmetric flow was observed for Reynolds numbers greater than about 36. In contrast viscoelasticity was found to stabilise the flow; setting β = 0.5 and We = 2 as typical values, resulted in symmetric flow up to a Reynolds number of about 46. We analyse these two cases in particular detail.     

On the confinement of a viscous fluid by means of a feedback external field

In this work we consider a planar stationary flow of an incompressible viscous fluid in a semi-infinite strip governed by the standard Stokes system. We show how this fluid can be stopped at a finite distance from the entrance of the semi-infinite strip by means of a feedback source depending in a sublinear way on the velocity field. This localization effect is proved by reducing the problem to a non-linear biharmonic type one for which the localization of solutions is obtained through the application of an energy method, in the spirit of the monograph by S.N. Antontsev, J.I. Díaz and S.I. Shmarev (Energy Methods for Free Boundary Problems: Applications to Non-Linear PDEs and Fluid Mechanics, Birkäuser, Boston, 2002). Since the presence of the non-linear terms defined by the source is not standard in fluid mechanics literature, we give also some results about the existence and uniqueness of weak solutions for this problem. To cite this article: S.N. Antontsev et al., C. R. Mecanique 330 (2002) 797–802.     

Sound propagation in acoustically lined elliptical ducts

Sound propagation in ducts with elliptical cross-sections can be described in terms of modes characterized by Mathieu functions of orders specified by the boundary conditions. For ducts with locally reacting liners there is coupling between modes because the admissible solutions are linear combinations of Mathieu functions of different orders and the eigenvalues are roots of an infinite determinant. The amount of mode coupling depends on the eccentricity of the duct. For the case of small eccentricity of the duct, approximate general solutions are derived and an example is discussed, where solutions are found.