Combined supercritical-fluid chromatography/mass spectrometry in the analysis of diuron in plasma using on-line phase-system switching

On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL.     

An interpretation of cortical maps in echolocating bats

Target parameters such as reflectivity, range, velocity, and angular position are represented by ordered maps of tuned cortical neurons in insectivorous bats. It is suggested that the response of each neuron in such a map is determined by a hypothesis test conditioned on a particular value of the mapped parameter. The excitation of each neuron is then interpreted as a sample value of a conditional log-likelihood ratio or a log-likelihood function. Interpolation between the samples, which is needed to find the parameter that maximizes the mapped function (e.g., the maximum likelihood parameter estimate), can be accomplished with overlapped tuning curves. An attempt to portray a sharp peak by a weighted sum of relatively broad neuronal tuning curves or interpolation functions results in excitatory center/inhibitory surround behavior. Facilitation or antifacilitation of neurons that are likely to be excited by succeeding observations can be used for sequential detection and tracking. Interpolation and pulse-to-pulse data storage capability are required to explain range jitter sensitivity and to allow for moving target indication in bat sonar. If a cortical map represents an ordered array of hypothesis tests, then many such tests are implemented in parallel when target parameters are unknown. Detection performance is then degraded relative to the idealized situation in which all parameters are specified. Performance in noise may thus appear to be much worse than that of an ideal detector, even if each hypothesis test is optimally implemented.     

Binary quantum logic and generating semigroups

A refined definition of basic concepts for logic describing physical systems is proposed. Within the suggested formalism of generating semigroups the active logic of questions and passive logic of answers are introduced. The objects for which both logics are isomorphic are called self-adequate. It is shown that the assumption of self-adequacy implies that the object is either quantum or classical. The possibility of application of the theory to non-self-adequate objects is discussed.     

Nonlinear effects of electrical transport in crystals with orbital degeneration

The influence of an electrical field on the charge transfer in crystals with orbital degeneration is investigated. An expression is obtained for the current density in crystals with narrow d-conduction bands in transition metal compounds. As the electrical field intensity increases, a current density maximum is observed with a subsequent section of negative differential conductivity. The results of the investigation agree qualitatively with experimental data.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 14–18, February, 1989.     

Conservation de la charge dans les codes PIC

This Note introduces a new integral form of the charge and current deposition scheme given in 1992 by Villasenor and Buneman, which permits the conservation of charge in PIC codes. This integral form extends directly to higher order spline shape factors, whose use produces less numerical noise. We thus get a discrete charge conserving method for high order shape factors. This method extends easily to nonuniform Cartesian grids for first order shape factors. To cite this article: R. Barthelmé, C. R. Acad. Sci. Paris, Ser. I 341 (2005).     

Effect of Conditions of Electric-Spark Dispersion of Zinc on the Quality of the Product Obtained

Influence exerted by additives introduced into the working solution, by iron or copper formedin electric-spark dispersion of these metals and zinc, on the quality of the products obtained in electric erosionwas studied.     

Semiempirical calculation of the fine structure of the indium ion

The fine-structure parameters of a series of configurations of the first ion of indium and the gyromagnetic ratios in intermediate coupling are calculated by a semiempirical method in the single-configuration approximation.     

Structuring Multi-attribute Value Hierarchies

The first stage in a multi-attribute value analysis is the development of a hierarchical structure of the attributes of the problem. This paper reports the process of developing such a structure for the problem of choosing a suitable mode of transport for radioactive waste. The initial hierarchy of attributes went through several stages of development as new insights emerged about the nature of the problem. Some of the reasons behind this restructuring are discussed, and several important questions about the structuring process are formulated.     

Collisional parameters of H2O lines: effects of vibration

A complex semiclassical model for the calculation of line widths and shifts of H₂O broadened by N₂, derived from the Robert and Bonamy approach, is tested by comparisons with measurements for selected transitions in various vibrational bands. The lines retained, which involve rotational states with Kc=J or J−1 have been chosen for two reasons. The first is that they show large variations of the widths with J and thus enable a severe test of the model. The second is that, as explained in this paper, they are well-suited for the study of the effects of vibration on the collisional parameters. The measured values have been extracted from an updated version of a database built years ago (JQSRT 52 (1994) 481) that contains all available measurements. Comparisons between experimental and calculated widths and shifts at room temperature illustrate the quality of the model and clearly demonstrate, for the first time, that there is a vibrational dependence of the broadening. Values of collisional parameters are first studied in fundamental bands. This shows that the theoretical approach accounts for most of the dependence of broadening and shifting on rotational quantum numbers: the variations of γ, which reach a factor of nearly 20 from low to high J values, are correctly accounted for by the model as are some specific features of the shifts δ. Analysis confirms that the bending and stretching vibrations have significantly different effects on δ, due to the vibrational dependence of the intermolecular potential. On the other hand, differences on the widths are rather small with slightly smaller broadening for lines of the bending band. Calculations show that there is a spectroscopic effect, due to the larger rotational constant A in the v₂=1 state. Calculations made for overtone bands involving numerous quanta of the stretching vibration are then presented. They predict that a significant dependence of the width should be observed for high J lines due to the effect of vibration on the interaction potential. This is confirmed by comparisons with measurements for lines involving a change of three and four quanta of stretching vibration.     

Methods for implementing the stream boundary condition in DSMC computations

In the direct simulation Monte‐Carlo (DSMC) method for simulating rarefied gas flows, the velocities of simulator particles that cross a simulation boundary and enter the simulation space are typically generated using the acceptance–rejection procedure that samples the velocities from a truncated theoretical velocity distribution that excludes low and high velocities. This paper analyses an alternative technique, where the velocities of entering particles are obtained by extending the simulation procedures to a region adjacent to the simulation space, and considering the movement of particles generated within that region during the simulation time step. The alternative method may be considered as a form of acceptance–rejection procedure, and permits the generation of all possible velocities, although the population of high velocities is depleted with respect to the theoretical distribution. Nevertheless, this is an improvement over the standard acceptance–rejection method. Previous implementations of the alternative method gave a number flux lower than the theoretical number required. Two methods for obtaining the correct number flux are presented. For upstream boundaries in high‐speed flows, the alternative method is more computationally efficient than the acceptance–rejection method. However, for downstream boundaries, the alternative method is extremely inefficient. The alternative method, with the correct theoretical number flux, should therefore be used in DSMC computations in favour of the acceptance–rejection method for upstream boundaries in high‐speed flows. Copyright © 2003 John Wiley & Sons, Ltd.