Improvements in the electrochemical generation of arsine at gold electrodes as a sample introduction strategy for arsenic determination in well-water samples by atomic absorption spectrometry

The development and evaluation of a cathode consisting of a gold electrode covered by a polyaniline film, PANI/Au modified electrode, for electrochemical generation of arsine is described. The efficiency of arsine production using the new electrode was ascertained by comparison with corresponding hydride generation atomic absorption spectroscopy determinations of arsenic (As) in aqueous standards. The PANI/Au modified electrodes provide better sensitivity, accuracy and precision than the pure Au cathodes. The PANI/Au cathodes were prepared by controlled electrodeposition cycles of polyaniline films on top of Au electrodes. Cathodes obtained after 10 electrodeposition cycles showed the best performance, while the ones obtained after five voltammetry cycles produced films too thin and those obtained after 20 voltammetry cycles produced films too thick for the purpose of this work. Under optimised conditions, the As limit of detection in aqueous solutions, according to the (3σ) criterion, was 2.48 µg L^?1. For accuracy determination, the modified electrode was applied to quantification of As(III) in acidified aqueous solutions of the certified standard reference material, NIST SRM 1643d, and in well-water samples containing possible interfering ions. Application of the Student’s t-test showed no significant difference between the expected and obtained results of the NIST SRM standard analysis at the 95% confidence level. Values for six replicate determinations of As(III) in the well-water samples showed close agreement with values obtained by analyses using hydride generation atomic absorption. Recoveries were in the range of 95–105% at test for acceptable accuracy in the analysis of real samples.     

A Popov-theory-based survey on digital control of infinite-dimensional systems with unboundedness

This paper represents a Popov-theory-based assessment of thecurrent status of the digital control of infinite–dimensionalsystems with certain unboundedness in control and/or observation,summarizing some results and indicating which, in the authors'opinion, would be the promising directions for future research.     

An adaptive control scheme for a continuous plant under Known output delay, unmodelled dynamics, and input saturation

This paper deals with robustness of adaptive control of continuoussystems subject to known output delay, input saturation, unmodelledlinear dynamics, and bounded disturbances. A simple gradient-typealgorithm with a relative deadzone is used. The relative deadzoneis built with an estimated contribution of the unmodelled dynamicsto the system output. The basic tool used for stability androbustness analysis is Gronwall's lemma.     

Exact dynamic stiffness elements based on one-dimensional higher-order theories for free vibration analysis of solid and thin-walled structures

In this paper, an exact dynamic stiffness formulation using one-dimensional (1D) higher-order theories is presented and subsequently used to investigate the free vibration characteristics of solid and thin-walled structures. Higher-order kinematic fields are developed using the Carrera Unified Formulation, which allows for straightforward implementation of any-order theory without the need for ad hoc formulations. Classical beam theories (Euler–Bernoulli and Timoshenko) are also captured from the formulation as degenerate cases. The Principle of Virtual Displacements is used to derive the governing differential equations and the associated natural boundary conditions. An exact dynamic stiffness matrix is then developed by relating the amplitudes of harmonically varying loads to those of the responses. The explicit terms of the dynamic stiffness matrices are also presented. The resulting dynamic stiffness matrix is used with particular reference to the Wittrick–Williams algorithm to carry out the free vibration analysis of solid and thin-walled structures. The accuracy of the theory is confirmed both by published literature and by extensive finite element solutions using the commercial code MSC/NASTRAN^®$\mathrm{MSC}/{\mathrm{NASTRAN}}^{\circledR }$.     

A correlation between the order parameters of rigid solutes dissolved in two nematic solvents and in a mixture of them

The orientational data of four rigid solutes dissolved in the nematic solvents ZLI1132, EBBA and in a 55wt% ZLI1132 + EBBA mixture have been obtained from proton NMR spectra at different temperatures and used to find a relationship between the solute order in the two nematics and in their mixture. A crossed comparison of the data shows that a simple linear relation, where the normalized weights of the combination are coincident with the molar fractions of ZLI1132 and EBBA in the mixture, gives excellent agreement independently of the solutes and temperatures. Consideration is given to the possibility of a generalization of the results to any mixture of two nematics.     

Ethnic Preferences and Residential Segregation: Theoretical Explorations Beyond Detroit

We are strongly supportive of Fossett's theoretical approach and modeling methodology, which uses computational methods to perform thought experiments that generate compelling insights into the enigma of persistent residential segregation in the U.S. We also agree with his theoretical results, which challenge the prevailing view among demographers that institutional discrimination is the essential cause. However, we think he did not go far enough. Fossett limited his analysis to a narrow region of the parameter space that corresponded to conditions observed in one city at one time. This precludes generalization to other times and places and exploration of theoretically motivated “what if” scenarios that trespass beyond the Detroit city limits. When we extended the parameter space, we noticed two interesting results. First, Fossett's “paradox of weak minority preferences” requires qualification. Disproportionate in-group preferences among minorities are indeed segregation-promoting, not integration-promoting, but they generally have less impact on segregation than the in-group preferences of the majority. Second, not only are exclusionary practices and institutional discrimination not necessary for segregation (as Fossett demonstrates), we show that in certain regions of the parameter space they are not even sufficient.     

Synthesis and characterization of a Gd(III) based contrast agent responsive to thiol containing compounds

A novel Gd(III) complex with a modified DO3A-like chelating cage has been synthesized and characterized as a candidate contrast agent responsive to the concentration of free thiols in tissues (essentially represented by reduced glutathione, GSH). The novel compound (called Gd-DO3AS-Act) bears a flexible linker ending with a 2-pyridyl-dithio group, that can promptly react with free thiols (XSH) to form mixed disulfides of the form Gd-DO3AS-SX. Compound Gd-DO3AS-Act is characterized by a millimolar relaxivity as high as 8.1 mM(-1) s(-1) (at 20 MHz, 25 degrees C and pH 7.4). Upon reaction with GSH, the Gd-DO3AS-SG covalent adduct is formed and the millimolar relaxivity drops to 4.1 mM(-1) s(-1). Such a decrease in relaxivity is explained on the basis of the formation of an intramolecular coordinative bond between one of the glutathionyl carboxyl groups and the Gd(III) centre, lowering the hydration state of the paramagnetic centre. (1)H-NMR dispersion profiles together with (17)O-NMR transverse relaxation time versus temperature profiles confirm that the hydration of the Gd(III) centre is strongly reduced ongoing from Gd-DO3AS-Act to the Gd-DO3AS-SG adduct. The relaxivity difference brought about by the reaction of Gd-DO3AS-Act with GSH can be enhanced up to 60% in the presence of poly-beta-cyclodextrin.