Disposable pipette extraction for gas chromatographic determination of codeine, morphine, and 6-monoacetylmorphine in vitreous humor

The availability of a sensitive and rapid analytical method for the determination of opiates, and other substances of forensic interest, in a variety of biological specimens is of utmost importance to forensic laboratories. Solid-phase extraction is very popular in the pre-treatment of forensic samples. Nevertheless, a new approach, disposable pipette extraction (DPX), is gaining increasing interest in sample preparation. DPX has already been applied to the analysis of drugs of abuse in common biological matrices, such as urine and blood, but has not yet been evaluated on alternative biological samples, such as vitreous humor. The objective of this study was to evaluate the applicability of DPX on the analysis of opiates in vitreous humor. The currently developed method is fast, reliable, and easy to perform. The sensitivity, precision, and accuracy are satisfactory. Recoveries obtained are within the range of 72-91%, whereas the sample volume of vitreous humor required is only 100 μL.     

Recovery rates in investment-grade pools of credit assets: A large deviations analysis

We consider the effect of recovery rates on a pool of credit assets. We allow the recovery rate to depend on the defaults in a general way. Using the theory of large deviations, we study the structure of losses in a pool consisting of a continuum of types. We derive the corresponding rate function and show that it has a natural interpretation as the favored way to rearrange recoveries and losses among the different types. Numerical examples are also provided.     

An effective Markov based approach for calculating the Limit Matrix in the analytic network process

Analytic network process is a multiple criteria decision analysis (MCDA) method that aids decision makers to choose among a number of possible alternatives or prioritize the criteria for making a decision in terms of importance. It handles both qualitative and quantitative criteria, that are compared in pairs, in order to forge a best compromise answer according to the different criteria and influences involved. The method has been widely applied and the literature review reveals a rising trend of ANP-related articles. The ‘power’ matrix method, a procedure necessary for the stability of the decision system, is one of the critical calculations in the mathematical part of the method. The present study proposes an alternative mathematical approach that is based on Markov chain processes and the well-known Gauss-Jordan elimination. The new approach obtains practically the same results as the power matrix method, requires slightly less time and number of calculations and handles effectively cyclic supermatrices, optimizing thus the whole procedure.     

Real-time monitoring of nanomolar binding to a cyclodextrin monolayer immobilized on a Si/SiO2/novolac surface using white light reflectance spectroscopy: the case of triclosan

The monitoring of the antibacterial agent triclosan binding at nanomolar concentration from an aqueous solution by employing a well-packed monolayer with a predetermined single orientation made of specifically synthesized 2,3-dimethyl-6-(undec-10-enamide)-6-deoxy-β-cyclodextrin (DMBUA) on a silicon wafer (Si/SiO(2)) coated with a novolac resin is reported. A white light reflectance spectroscopy (WLRS) setup was used for the real-time monitoring of the DMBUA deposition and triclosan binding processes. Film thicknesses obtained by WLRS were in very good agreement with the ones measured by X-ray reflectivity (XRR) experiments. Triclosan binds strongly to the DMBUA monolayer (logK(assoc)=6.68). NMR studies in aqueous solution indicated that the chlorophenolyl ring rather than the dichlorophenyl ring is preferentially inserted into DMBUA cups. The current detecting system that requires no tedious surface chemistry, no thiolated cyclodextrins, no gold surfaces, and no expensive equipment may be useful in capturing small molecules and may permit various applications, e.g., preparation of antimicrobial surfaces.     

A constrained approach to multiscale stochastic simulation of chemically reacting systems

Stochastic simulation of coupled chemical reactions is often computationally intensive, especially if a chemical system contains reactions occurring on different time scales. In this paper, we introduce a multiscale methodology suitable to address this problem, assuming that the evolution of the slow species in the system is well approximated by a Langevin process. It is based on the conditional stochastic simulation algorithm (CSSA) which samples from the conditional distribution of the suitably defined fast variables, given values for the slow variables. In the constrained multiscale algorithm (CMA) a single realization of the CSSA is then used for each value of the slow variable to approximate the effective drift and diffusion terms, in a similar manner to the constrained mean-force computations in other applications such as molecular dynamics. We then show how using the ensuing Fokker-Planck equation approximation, we can in turn approximate average switching times in stochastic chemical systems.     

A theoretical study of the XP and NEXAFS spectra of alanine: gas phase molecule, crystal, and adsorbate at the ZnO(10 ̅10) surface

The adsorption of alanine on the mixed-terminated ZnO(10 ?10) surface is studied by means of quantum-chemical ab initio calculations. Using a finite cluster model and the adsorption geometry as obtained both by periodic CPMD and embedded cluster calculations, the C1s, N1s and O1s X-ray photoelectron spectra (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectra are calculated for single alanine molecules on ZnO(10 ?10). These spectra are compared with the spectra calculated for alanine in the gas phase and in its crystalline form and with experimental XPS and NEXAFS data for the isolated alanine molecule and for alanine adsorbed on ZnO(10 ?10) at multilayer and monolayer coverage. The excellent agreement between the experimental and calculated XP and NEXAFS spectra confirms the calculated adsorption geometry: A single alanine molecule is bound to ZnO(10 ?10) in a dissociated bidentate form with the two O atoms of the acid group bound to two Zn atoms of the surface and the proton transferred to one O atom of the surface. Other possible structures, such as adsorption of alanine in one of its neutral or zwitterionic forms in which the proton of the -COOH group remains at this group or is transferred to the amino group, can be excluded since they would give rise to quite different XP spectra. In the multilayer coverage regime, on the other hand, alanine is in its crystalline form as is also shown by the analysis of the XP spectra.     

Density symmetries for a class of 2-D diffusions with applications to finance

We study densities of two-dimensional diffusion processes with one non-negative component. For such diffusions, the density may explode at the boundary, thus making a precise specification of the boundary condition in the corresponding forward Kolmogorov equation problematic. We overcome this by extending a classical symmetry result for densities of one-dimensional diffusions to our case, thereby reducing the study of forward equations with exploding boundary data to the study of a related backward equation with non-exploding boundary data. We also discuss applications of this symmetry for option pricing in stochastic volatility models and in stochastic short rate models.     

On the Effect of Misspecifying the Density Ratio Model

The density ratio model specifies that the log-likelihood ratio of two unknown densities is of known linear form which depends on some finite dimensional parameters. The model can be broadened to allow for m-samples in a quite natural way. Estimation of both parametric and nonparametric part of the model is carried out by the method of empirical likelihood. However the assumed linear form has an impact on the estimation and testing for the parametric part. The goal of this study is to quantify the effect of choosing an incorrect linear form and its impact to inference. The issue of misspecification is addressed by embedding the unknown linear form to some parametric transformation family which yields ultimately to its identification. Simulated examples and data analysis integrate the presentation.     

New synthesis of hexamethyltungsten(VI); hexamethylrhenium(VI) and dioxotrimethylrh enium(VII)

A new synthesis of hexamethyltungsten involves the reaction of WCl₆ and AlMe₃, while interaction of AlMe₃ and ReOMe₄ gives ReMe₆; a dioxorhenium(VII) methyl, ReO₂ Me₃, is reported.     

Integer points on the curve

We completely solve diophantine equations of the form where is a positive integer, using a reduction to some quartic elliptic equations, which can be solved with well known methods.