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.     

A two-dimensional time-domain finite element formulation for periodic structures

A formulation is presented for a two-dimensional time-domain finite-element method (FEM-TD) that incorporates periodic boundaries. The specifics of the method are shown for scattering problems, but it should be straightforward to extend it to radiation problems. The method solves for a transformed field variable (instead of solving directly for the electric field) in order to easily enable periodic boundary conditions in the time domain. The accuracy and stability of the method is demonstrated by a series of examples where the new formulation is compared with reference solutions. Very accurate results are obtained when the excitation (frequency range) and the geometry are such that no higher order Floquet modes are present. The accuracy is degraded in the presence of higher order modes due to the rather simple absorbing boundary condition that is used with the present formulation. The method is found to be stable even for angles of incidence close to grazing.     

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.     

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.     

Hot-carrier reliability of 20V MOS transistors in 0.13 μm CMOS technology

This paper presents results of reliability investigation of 20 V N-Drift MOS transistor in 0.13 μm CMOS technology. Due to high performances required for CMOS applications, adding high voltage devices becomes a big challenge to guarantee the reliability criteria. In this context, new reliability approaches are needed. Safe Operating Area are defined for switch, V_ds limited and V_gs limited applications in order to improve circuit designs. For V_ds limited applications, deep doping dose effects in drift area are investigated in correlation to lifetime evaluations based on device parameter shifts under hot carrier stressing. To further determine the amount and locations of hot carriers injections, accurate 2D technological and electrical simulations are performed and permit to select the best compromise between performance and reliability for N-Drift MOS transistor.     

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.     

Photoinitiators with functional groups. VII. Covalently bonded camphorquinone—amines

Camphorquinone (CQ), a widely used photoinitiator (PI) in dental applications, was covalently bonded to aromatic amines to enhance the rate of electron and proton transfer effect due to the close vicinity of the diketone and the amine group. 10‐bromocamphorquinone and 10‐bromomethylcamphorquinone were selected as suitable precursors for esterification with the carboxyl group containing aromatic amines based on 4‐dimethylaminobenzoic acid. Properties of the new photoinitiating systems were investigated by UV spectroscopy and differential scanning photocalorimetry in lauryl acrylate. Compared to physical mixtures, in all cases similar or even better performance was obtained. Surprisingly, 10‐acetyl derivatives 7 – 9 and 18 especially, were found to be highly reactive. Compared to CQ/ethyl 4‐dimethylaminobenzoate, the rate of photopolymerization was increased by a factor of up to 2. Intramolecular reaction was confirmed by photo‐differential scanning calorimetry experiments with varying PI concentrations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4948–4963, 2004     

Photochemical attachment of polymers on planar surfaces with a covalently anchored monolayer of a novel naphthyl ketone photochemical radical generator

A monolayer of covalently anchored, novel, binaphthyl ketone is used as a surface‐confined photochemical radical generator (PRG) for anchoring a variety of polymers to silicon surfaces. The precursor PRG is synthesized by the application of a facile and novel method for the oxidation of sterically hindered benzylic hydrocarbons to carbonyl compounds. Oxidation was carried out with a stoichiometric amount of potassium peroxydisulfate, in the presence of a catalytic amount of copper sulfate in an acetonitrile/water mixture. The PRG synthesized is characterized by ¹H NMR, UV, and Fourier transform infrared (FTIR). The covalently attached monolayers are characterized by X‐ray photoelectron spectroscopy, ellipsometry, and water contact angle measurements. The method developed is applicable to the preparation of a monolayer of a variety of polymers on a wide range of substrates carrying surface hydroxyl groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5413–5423, 2004