Simultaneous analysis of pesticides from different chemical classes by using a derivatisation step and gas chromatography-mass spectrometry

This work presents a new method to analyse simultaneously by GC–MS 31 pesticides from different chemical classes (2,4 D, 2,4 MCPA, alphacypermethrin, bifenthrin, bromoxynil, buprofezin, carbaryl, carbofuran, clopyralid, cyprodinil, deltamethrin dicamba, dichlobenil, dichlorprop, diflufenican, diuron, fenoxaprop, flazasulfuron, fluroxypyr, ioxynil, isoxaben, mecoprop-P, myclobutanil, oryzalin, oxadiazon, picloram, tau-fluvalinate tebuconazole, triclopyr, trifluralin and trinexapac-p-ethyl). This GC–MS method will be applied to the analysis of passive samplers (Tenax^® tubes and SPME fiber) used for the evaluation of the indoor and outdoor atmospheric contamination by non-agricultural pesticides. The method involves a derivatisation step for thermo-labile or polar pesticides. Different agents were tested and MtBSTFA (N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide), a sylilation agent producing very specific fragments [M−57], was retained. However, diuron could not be derivatised and the isocyanate product was used for identification and quantification. Pesticides which did not need a derivatisation step were not affected by the presence of the derivatisation agent and they could easily be analysed in mixture with derivatised pesticides. The method can be coupled to a thermal-desorption unit or to SPME extraction for a multiresidue analysis of various pesticides in atmospheric samples.     

A neutron diffraction study of the high pressure structural phase transition in (CD3ND3)2MnCl4

Abstract

High-pressure neutron diffraction experiments have been performed at room temperature on a powdered sample of the perovskite type-layer compound (CD₃ND₃)₂MnCl₄. A phase transition from the orthorhombic room-temperature phase (ORT) to a new high-pressure phase (HP) is demonstrated at 20.5 ± 0.2 kbars. A monoclinic unit cell with lattice parameters a = 6.824 (5) Å; b = 7.409 (8) Å c = 17.126 (12) Å and β = 82.94(9)° has been inferred for the HP phase, consistent with a two-dimensional perovskite-type structure. The HP phase appears to be much more compact than ORT; it is characterized, in particular, by an important compression (?10%) of the inter-layer distance. Space groups P2/c or P2₁/c consistent with the experimental data have been deduced for the HP phase, after group theoretical considerations based on shear transformation and order-disorder mechanisms.     

Stochastic Two-Dimensional Hydrodynamical Systems: Wong-Zakai Approximation and Support Theorem

We deal with a class of abstract nonlinear stochastic models with multiplicative noise, which covers many 2D hydrodynamical models including the 2D Navier–Stokes equations, 2D MHD models and 2D magnetic Bénard problems as well as some shell models of turbulence. Our main result describes the support of the distribution of solutions. Both inclusions are proved by means of a general Wong–Zakai type result of convergence in probability for nonlinear stochastic PDEs driven by a Hilbert-valued Brownian motion and some adapted finite dimensional approximation of this process.     

SUMS: synchronous undulator–monochromator scans at Synchrotron Soleil

A strategy for performing synchronous undulator–monochromator scans (SUMS) compatible with the control system of Synchrotron Soleil has been developed. The implementation of the acquisition scheme has required the development of an electronic interface between the undulator and the beamline. The characterization of delays and jitters in the synchronous movement of various motor axes has motivated the development of a new electronic synchronization scheme among various axes, including the case when one of the axes is electronically accessible in `read‐only' mode. A software prototype has been developed to allow the existing hard continuous software to work in user units. The complete strategy has been implemented and successfully tested at the TEMPO beamline.     

Stochastic 2D Hydrodynamical Type Systems: Well Posedness and Large Deviations

We deal with a class of abstract nonlinear stochastic models, which covers many 2D hydrodynamical models including 2D Navier-Stokes equations, 2D MHD models and the 2D magnetic Bénard problem and also some shell models of turbulence. We state the existence and uniqueness theorem for the class considered. Our main result is a Wentzell-Freidlin type large deviation principle for small multiplicative noise which we prove by a weak convergence method.     

Anisotropic field dependence of the magnetic transition in Cu2Te2O5Br2

In this paper, we present the results of measurements of the thermal conductivity of Cu2Te2O5Br2, a compound where tetrahedra of Cu2+ ions carrying S=1/2 spins form chains along the c-axis of the tetragonal crystal structure. The thermal conductivity was measured along both the c- and the a-direction as a function of temperature between 3 and 300 K and in external magnetic fields H up to 69 kOe, oriented both parallel and perpendicular to the c-axis. Distinct features of (T) were observed in the vicinity of TN=11.4 K in zero magnetic field. These features are unaltered in external fields which are parallel to the c-axis, but are more pronounced when a field is applied perpendicularly to the c-axis. The transition temperature increases upon enhancing the external field, but only if the field is oriented along the a-axis.     

Mössbauer spectroscopic study of iron phosphate catalysts used in selective oxidation

Three iron phosphate compounds FePO₄, Fe₂P₂O₇ and Fe₇(PO₄)₆ have been synthesized and studied as catalysts for the oxidative dehydrogenation of isobutyric acid to methacrylic acid. Mössbauer spectroscopic characterization of the solids before and after catalytic reaction has allowed us to show that the starting phases were transformed in the conditions of reaction and that a new phase was formed. This new phase is a mixed Fe³⁺ and Fe²⁺ phosphate with a Fe³⁺/Fe²⁺ ratio of 1.8±0.2 with Mössbauer parameters: δ₁=0.47 ± 0.05, Δ₁=0.68± 0.02 mm.s^-1 and δ₂=1.20 ± 0.05, Δ₂=2.73±0.02 mm.s^-1. This new phase appears to be elective for methacrylic acid formation.     

An asymptotic non-linear model for thin-walled rodsUn modèle asymptotique non-linéaire de poutres à parois minces

In this paper, we present a non-linear one-dimensional model for thin-walled rods with open strongly curved cross-section, obtained by asymptotic methods. A dimensional analysis of the non-linear three-dimensional equilibrium equations lets appear dimensionless numbers which reflect the geometry of the structure and the level of applied forces. For a given force level, the order of magnitude of the displacements and the corresponding one-dimensional model are deduced by asymptotic expansions. To cite this article: L. Grillet et al., C. R. Mecanique 332 (2004).     

Development,Validation, and Comparison of Two Mass Spectrometry Methods (LC-MS/HRMS and LC-MS/MS) for the Quantification of Rituximab in Human Plasma

Rituximab is a chimeric immunoglobulin G1-kappa (IgG1κ) antibody targeting the CD20 antigen on B-lymphocytes. Its applications are various, such as for the treatment of chronic lymphoid leukemia or non-Hodgkin’s lymphoma in oncology, and it can also be used in the treatment of certain autoimmune diseases. Several studies support the interest in therapeutic drug monitoring to optimize dosing regimens of rituximab. Thus, two different laboratories have developed accurate and reproductive methods to quantify rituximab in human plasma: one using liquid chromatography quadripolar tandem mass spectrometer (LC-MS/MS) and the other, liquid chromatography orbitrap tandem mass spectrometer (LC-MS/HRMS). For both assays, quantification was based on albumin depletion or IgG-immunocapture, surrogate peptide analysis, and full-length stable isotope-labeled rituximab. With LC-MS/MS, the concentration range was from 5 to 500 µg/mL, the within- and between-run precisions were <8.5%, and the limit of quantitation was 5 µg/mL. With LC-MS/HRMS, the concentration range was from 10 to 200 µg/mL, the within- and between-run accuracy were <11.5%, and the limit of quantitation was 2 µg/mL. Rituximab plasma concentrations from 63 patients treated for vasculitis were compared. Bland–Altman analysis and Passing–Bablok regression showed the interchangeability between these two methods. Overall, these methods were robust and reliable and could be applied to routine clinical samples.     

Protein tyrosine phosphatase oligomerization studied by a combination of 15N NMR relaxation and 129Xe NMR. Effect of buffer containing arginine and glutamic acid

15N NMR relaxation and 129Xe NMR chemical shift measurements offer complementary information to study weak protein-protein interactions. They have been applied to study the oligomerization equilibrium of a low-molecular-weight protein tyrosine phosphatase in the presence of 50 mM arginine and 50 mM glutamic acid. These experimental conditions are shown to enhance specific protein-protein interactions while decreasing nonspecific aggregation. In addition, 129Xe NMR chemical shifts become selective reporters of one particular oligomer in the presence of arginine and glutamic acid, indicating that a specific Xe binding site is created in the oligomerization process. It is suggested that the multiple effects of arginine and glutamic acid are related to their effective excluded volume that favors specific protein association and the destabilization of partially unfolded forms that preferentially interact with xenon and are responsible for nonspecific protein aggregation.