Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

Memory effects in gas chromatographic detection with a microwave-induced plasma

Capillary gas chromatography coupled to microwave-inducedplasma detection furnishes sensitivity adequate for trace analysis when the signal is monitored at a carbon emission line. Work performed with one of these systems at high electronic gain for the carbon signal has revealed solvent band widths in excess of four minutes; these impeded quantification of peaks eluting after the solvent. This report discusses two phenomena which could be related to the unexpected intensity of this solvent response: photomultiplier tube saturation and carbon deposits in the quartz plasma discharge tube.     

Mercury removal from aqueous solution and flue gas by adsorption on activated carbon fibres

The use of two activated carbon fibres, one laboratorial sample prepared from a commercial acrylic textile fibre and one commercial sample of Kynol^®, as prepared/received and modified by reaction with powdered sulfur and H₂S gas in order to increase the sulfur content were studied for the removal of mercury from aqueous solution and from flue gases from a fluidized bed combustor. The sulfur introduced ranged from 1 to 6 wt.% depending on the method used. The most important parameter for the mercury uptake is the type of sulfur introduced rather than the total amount and it was found that the H₂S treatment of ACF leads to samples with the highest mercury uptake, despite the lower sulfur amount introduced. The modified samples by both methods can remove HgCl₂ from aqueous solutions at pH 6 within the range 290-710 mg/g (ACF) which can be favourably compared with other studies already published. The use of a filter made with an activated carbon fibre modified by powdered sulfur totally removed the mercury species present in the flue gases produced by combustion of fossil fuel.     

Long-range predictive adaptive fuzzy relational control

A class of long-range predictive adaptive fuzzy relational controllers is presented. The plant behavior is described over an extended time horizon by a fuzzy relational model which is identified based on input-output closed-loop observations of the plant variables. In this class of adaptive controllers the control law attempts to minimize a quadratic cost over an extended control horizon. When used with linear models, this approach has revealed a significant potential for overcoming the limitations of one-step ahead schemes, such as the stabilization of non-minimum phase plants. Here, a uniform framework is adopted for implementing both the fuzzy model and the fuzzy controller, namely distributed fuzzy relational structures gaining from their massive parallel processing features and from the learning capabilities typical of the connectivist approaches. Issues such as maintenance during the adaptation process of the meaning of linguistic terms used at both fuzzy systems interfaces are addressed, namely by introducing a new design methodology for on-line fuzzy systems interface adaptation. The examples presented reinforce the claim of the usefulness of this new approach.     

Analysis of a demodulation system for Fiber Bragg Grating sensors using two fixed filters

The analysis of a demodulation system for Fiber Bragg Grating sensors based on two fixed spectral filters has been carried out both theoretically and experimentally. Different system configurations were analyzed by modifying the spectral position of the filters as well as the optical power-level of the signal reaching the two photo-detectors. Measurements with integration times that varied from 0.01 to 1 s have been compared with the low-frequency limit predicted for long-term operation. Comparisons between simulated and experimental results show good agreement, and extrapolations indicate that it should be possible to achieve an operating spectrum range of the order of 7 nm, with uncertainties equivalent to less than 2 pm in measurements of the sensor peak position.     

Transport properties of alkyltrimethylammonium bromide surfactants in aqueous solutions

Differential mutual diffusion coefficients of n-alkyltrimethylammonium bromides [CH₃(CH₂)_n–1N(CH₃)₃Br, C_nTAB] (n=10, 12, 14, 16) have been measured in aqueous solutions at 298.15 K using a conductimetric cell and an automatic apparatus to follow diffusion. The cell is based on an open-ended capillary, and the technique follows the diffusion process by measuring the resistance of a solution inside the capillaries at various times. The electrical conductances of those solutions have also been measured to calculate the critical micellar concentration (cmc). Thermodynamic analysis of the data suggests that the free ion concentration decreases at concentrations above the cmc, in agreement with theoretical predictions. The obtained values of the micellization parameters were used to model the mutual diffusion coefficients of C_nTAB aqueous solutions.     

High yield thiolation of iodobenzene catalyzed by the phosphinite nickel PCP pincer complex: [NiCl{C6H3-2,6-(OPPh2)2}]

[NiCl{C₆H₃-2,6-(OPPh₂)₂}] efficiently catalyzes the thiolation of iodobenzene with a broad scope of disulfides in the presence of zinc, the coupled products are obtained in excellent and in many cases nearly quantitative yields.