Analyse simultanée des hormones stéroïdiennes et leurs formes chimiques dans les matrices d'eau et d'urine par SPE-LC-MS/MS en ligne.

Dans les dernières années, les perturbateurs endocriniens ont été observés dans les rivières qui reçoivent des entrées importantes d’eaux usées. Parmi les perturbateurs endocriniens, les hormones stéroïdiennes naturelles et synthétiques sont des composés dont le potentiel d'imiter ou d'interférer avec les fonctions hormonales normales (développement, croissance et reproduction), est reconnu même au niveau ultra-traces (ng L-1). Bien que les hormones conjuguées soient moins actives que les hormones libres, elles peuvent être clivées et redevenir libres une fois exposées aux processus microbiens avant ou pendant le traitement des eaux usées. En raison de la nécessité d'identifier et de quantifier ces composés dans l'eau, une nouvelle méthode, entièrement automatisée, a été développée pour la détermination simultanée des deux formes de plusieurs hormones stéroïdiennes (conjuguées et libres) dans les matrices d'eau et dans l’urine des femmes. La méthode est basée sur l'extraction en phase solide couplée en ligne à la chromatographie liquide et la spectrométrie de masse en tandem (SPE-LC-MS/MS). Plusieurs paramètres ont été évalués dans le but d'optimiser l'efficacité de la méthode, tels que le type et le débit de la phase mobile, des différentes colonnes de SPE et de chromatographie, ainsi que différentes sources et modes d'ionisation des échantillons pour la MS. La méthode démontre une bonne linéarité (R2 > 0.993), ainsi qu'une précision avec un coefficient de variance inférieure à 10%. Les limites de quantification varient d’un minimum de 3 à 15 ng L-1 pour un volume d'injection entre 1 mL et 5 mL et le recouvrement des composés varie de 72 % à 117 %.

Elemental Analysis of Biological Matrices by Laser Ablation High Resolution Inductively Coupled Plasma Mass Spectrometry (LA-HR-ICP-MS) and High Resolution Inductively Coupled Plasma Mass Spectrometry (HR-ICP-MS)

The need for elemental analysis of biological matrices such as bone, teeth, and plant matter for sourcing purposes has emerged within the forensic and geochemical laboratories. Trace elemental analyses for the comparison of aterials such as glass by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS has been shown to offer a high degree of discrimination between different manufacturing sources. Unit resolution ICP-MS instruments may suffer from some polyatomic interferences including 40Ar16O+, 40Ar16O1H+, and 40Ca16O+ that affect iron measurement at trace levels. Iron is an important element in the analysis of glass and also of interest for the analysis of several biological matrices. A comparison of the nalytical performance of two different ICP-MS systems for iron analysis in glass for determining the method detection limits (MDLs), accuracy, and precision of the measurement is presented. Acid digestion and laser ablation methods are also compared. Iron polyatomic interferences were reduced or resolved by using dynamic reaction cell and high resolution ICP-MS. MDLs as low as 0.03 ìg g-1 and 0.14 ìg g-1 for laser ablation and solution based analyses respectively were achieved. The use of helium as a carrier gas demonstrated improvement in the detection limits of both iron isotopes (56Fe and 57Fe) in medium resolution for the HR-ICP-MS and with a dynamic reaction cell (DRC) coupled to a quadrupole ICP-MS system. The development and application of robust analytical methods for the quantification of trace elements in biological matrices has lead to a better understanding of the potential utility of these measurements in forensic chemical analyses. Standard reference materials (SRMs) were used in the development of an analytical method using HR-ICP-MS and LA-HR-ICP-MS that was subsequently applied on the analysis of real samples. Bone, teeth and ashed marijuana samples were analyzed with the developed method. Elemental analysis of bone samples from 12 different individuals provided discrimination between individuals, when femur and humerus bones were considered separately. Discrimination of 14 teeth samples based on elemental composition was achieved with the exception of one case where samples from the same individual were not associated with each other. The discrimination of 49 different ashed plant (cannabis)samples was achieved using the developed method.

US Asset Backed Securities – Risk Symmetric Disclosures

This chapter examines disclosures of US asset-backed securities in terms of information asymmetry theory and risk symmetry.

Superregular matrices and applications to convolutional codes

The main results of this paper are twofold: the first one is a matrix theoretical result. We say that a matrix is superregular if all of its minors that are not trivially zero are nonzero. Given a a×b, a ≥ b, superregular matrix over a field, we show that if all of its rows are nonzero then any linear combination of its columns, with nonzero coefficients, has at least a−b + 1 nonzero entries. Secondly, we make use of this result to construct convolutional codes that attain the maximum possible distance for some fixed parameters of the code, namely, the rate and the Forney indices. These results answer some open questions on distances and constructions of convolutional codes posted in the literature.

Symmetric Interior Penalty DG Methods for the Compressible Navier-Stokes Equations I: Method Formulation

In this article we consider the development of discontinuous Galerkin finite element methods for the numerical approximation of the compressible Navier-Stokes equations. For the discretization of the leading order terms, we propose employing the generalization of the symmetric version of the interior penalty method, originally developed for the numerical approximation of linear self-adjoint second-order elliptic partial differential equations. In order to solve the resulting system of nonlinear equations, we exploit a (damped) Newton-GMRES algorithm. Numerical experiments demonstrating the practical performance of the proposed discontinuous Galerkin method with higher-order polynomials are presented.

Symmetric Interior Penalty DG Methods for the Compressible Navier-Stokes Equations II: Goal--Oriented A Posteriori Error Estimation

In this article we consider the application of the generalization of the symmetric version of the interior penalty discontinuous Galerkin finite element method to the numerical approximation of the compressible Navier--Stokes equations. In particular, we consider the a posteriori error analysis and adaptive mesh design for the underlying discretization method. Indeed, by employing a duality argument (weighted) Type I a posteriori bounds are derived for the estimation of the error measured in terms of general target functionals of the solution; these error estimates involve the product of the finite element residuals with local weighting terms involving the solution of a certain dual problem that must be numerically approximated. This general approach leads to the design of economical finite element meshes specifically tailored to the computation of the target functional of interest, as well as providing efficient error estimation. Numerical experiments demonstrating the performance of the proposed approach will be presented.

Fast assembly of fock matrices utilising symmetry properties of the basis set

A method of assembling the elements of the Fock matrix is described which is a modification of that due to Dacre. Lists of symmetry equivalent one-electron integrals are used as pointers to abbreviate the process of collecting two-electron integrals into the Fock matrix.

The analysis and detection of new psychoactive substances in biological matrices

New psychoactive substances (NPSs) have appeared on the recreational drug market at an unprecedented rate in recent years. Many are not new drugs but failed products of the pharmaceutical industry. The speed and variety of drugs entering the market poses a new complex challenge for the forensic toxicology community. The detection of these substances in biological matrices can be difficult as the exact compounds of interest may not be known. Many NPS are sold under the same brand name and therefore users themselves may not know what substances they have ingested. The majority of analytical methods for the detection of NPSs tend to focus on a specific class of compounds rather than a wide variety. In response to this, a robust and sensitive method was developed for the analysis of various NPS by solid phase extraction (SPE) with gas chromatography mass spectrometry (GCMS). Sample preparation and derivatisation were optimised testing a range of SPE cartridges and derivatising agents, as well as derivatisation incubation time and temperature. The final gas chromatography mass spectrometry method was validated in accordance with SWGTOX 2013 guidelines over a wide concentration range for both blood and urine for 23 and 25 analytes respectively. This included the validation of 8 NBOMe compounds in blood and 10 NBOMe compounds in urine. This GC-MS method was then applied to 8 authentic samples with concentrations compared to those originally identified by NMS laboratories. The rapid influx of NPSs has resulted in the re-analysis of samples and thus, the stability of these substances is crucial information. The stability of mephedrone was investigated, examining the effect that storage temperatures and preservatives had on analyte stability daily for 1 week and then weekly for 10 weeks. Several laboratories identified NPSs use through the cross-reactivity of these substances with existing screening protocols such as ELISA. The application of Immunalysis ketamine, methamphetamine and amphetamine ELISA kits for the detection of NPS was evaluated. The aim of this work was to determine if any cross-reactivity from NPS substances was observed, and to determine whether these existing kits would identify NPS use within biological samples. The cross- reactivity of methoxetamine, 3-MeO-PCE and 3-MeO-PCP for different commercially point of care test (POCT) was also assessed for urine. One of the newest groups of compounds to appear on the NPS market is the NBOMe series. These drugs pose a serious threat to public health due to their high potency, with fatalities already reported in the literature. These compounds are falsely marketed as LSD which increases the chance of adverse effects due to the potency differences between these 2 substances. A liquid chromatography tandem mass spectrometry (LC-MS/MS) method was validated in accordance with SWGTOX 2013 guidelines for the detection for 25B, 25C and 25I-NBOMe in urine and hair. Long-Evans rats were administered 25B-, 25C- and 25I-NBOMe at doses ranging from 30-300 µg/kg over a period of 10 days. Tail flick tests were then carried out on the rats in order to determine whether any analgesic effects were observed as a result of dosing. Rats were also shaved prior to their first dose and reshaved after the 10-day period. Hair was separated by colour (black and white) and analysed using the validated LC-MS/MS method, assessing the impact hair colour has on the incorporation of these drugs. Urine was collected from the rats, analysed using the validated LC-MS/MS method and screened for potential metabolites using both LC-MS/MS and quadrupole time of flight (QToF) instrumentation.

Modal Control of Vibration in Rotating Machines and Other Generally Damped Systems

Second order matrix equations arise in the description of real dynamical systems. Traditional modal control approaches utilise the eigenvectors of the undamped system to diagonalise the system matrices. A regrettable consequence of this approach is the discarding of residual o-diagonal terms in the modal damping matrix. This has particular importance for systems containing skew-symmetry in the damping matrix which is entirely discarded in the modal damping matrix. In this paper a method to utilise modal control using the decoupled second order matrix equations involving nonclassical damping is proposed. An example of modal control sucessfully applied to a rotating system is presented in which the system damping matrix contains skew-symmetric components.

Modal Control of Vibration in Rotating Machines and Other Generally Damped Systems

Second order matrix equations arise in the description of real dynamical systems. Traditional modal control approaches utilise the eigenvectors of the undamped system to diagonalise the system matrices. A regrettable consequence of this approach is the discarding of residual off-diagonal terms in the modal damping matrix. This has particular importance for systems containing skew-symmetry in the damping matrix which is entirely discarded in the modal damping matrix. In this paper a method to utilise modal control using the decoupled second order matrix equations involving non-classical damping is proposed. An example of modal control successfully applied to a rotating system is presented in which the system damping matrix contains skew-symmetric components.