Preconcentration of trace antimony in tap and sea water on activated alumina. Determination by graphite furnace atomic absorption spectrometry

Summary A method is described for antimony preconcentration based on retention on a column of activated alumina. Recovery is 80% when no pH-control and 4 mol/l HCl as eluent are used. The preconcentration factor is 400. The method was applied to the determination of antimony in spiked tap and sea water. The analytical performance of the method is discussed.     

Space–time integrated least squares: a time‐marching approach

A time‐marching formulation is derived from the space–time integrated least squares (STILS) method for solving a pure hyperbolic convection equation and is numerically compared to various known methods. Copyright © 2004 John Wiley & Sons, Ltd.     

Nickel as a chemical modifier for sensitivity enhancement and fast atomization processes in electrothermal atomic absorption spectrometric determination of cadmium in biological and environmental samples.

A systematic study of the efficiency of protons, Ni, Pd and Th as chemical modifiers for the determination of cadmium by electrothermal atomic absorption spectrometry (ETAAS) using fast temperature programs was made for platform atomization. A comparison was made in terms of the salt type, absorbance-time profiles and elimination of the sodium chloride interference. The results were adapted to develop a method for the ETAAS determination of cadmium in biological and environmental samples. The highest sensitivity to determine cadmium in biological and environmental samples was obtained using nickel (together with protons) as a chemical modifier. The accuracy of the method was tested by the determination of cadmium in different certified reference materials. The best detection limit and the characteristic mass of Cd were found to be 0.03 ng mL(-1) and 0.35 pg, respectively.     

Voltammetric determination of methyl parathion, ortho, meta and para nitrophenol with a carbon paste electrode modified with C18

Summary The determination of methyl-parathion (MPT), ortho (ONP), meta (MNP) and para nitrophenol (PNP) has been studied by differential pulse voltammetry with a carbon-paste electrode modified with 50% (w/w) of C₁₈. A study of the influence of the pH in the preconcentration cell and the measurement cell was carried out for an electrode with 50% modifier and an accumulation time of 5 min. The voltammograms were recorded with a sweep rate of 40 mV s^–1 and a pulse amplitude of 50 mV. With the optimum conditions of pH for both of the steps, various other variables were studied. The variables for each compound were optimized and the possibility of application to the determination of a mixture of the four compounds was investigated. The determination limits found for all the compounds are: 2 ng ml^–1 for ONP, 5 ng ml^–1 for MNP, 4.3 ng ml^–1 for PNP and 7.9 ng ml^–1 for MPT. The method was applied to samples of a small lake which gathers rain water and water filtered from land on which cereals are grown.     

The phase diagram of the lyotropic nematic mesophase in the TTAB/NaBr/water system

The phase diagram of the nematic mesophase present in the tetradecyltrimethylammonium bromide/sodium bromide/water ternary system was determined. A calamitic nematic mesophase (N_C) was observed which extends to very high concentrations of electrolyte. The order parameters of the surfactant head group in the mesophases were studied by the NMR quadrupolar splitting of the deuterated surfactant. On increasing the temperature of nematic mesophases with low electrolyte concentrations, a phase separation occurs with the formation of a more highly ordered hexagonal phase and an isotropic phase. Diffusion measurements of the isotropic micellar solution by the NMR PFG method were used to estimate hydrodynamic radii at low surfactant concentrations and to study micelle diffusion as the concentration of the surfactant was increased to the liquid crystalline region. At higher surfactant concentrations, the diffusion coefficient reached a limiting value. The calamitic nematic mesophase in this surfactant/electrolyte/water system appears to be formed by long wormlike micelles.     

Synthesis and characterization of functional gradient copolymers of allyl methacrylate and butyl acrylate

Functional spontaneous gradient copolymers of allyl methacrylate (A) and butyl acrylate (B) were synthesized via atom transfer radical polymerization. The copolymerization reactions were carried out in toluene solutions at 100 °C with methyl 2‐bromopropionate as the initiator and copper bromide with N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalyst system. Different aspects of the statistical reaction copolymerizations, such as the kinetic behavior, crosslinking density, and gel fraction, were studied. The gel data were compared with Flory's gelation theory, and the sol fractions of the synthesized copolymers were characterized by size exclusion chromatography and nuclear magnetic resonance spectroscopy. The copolymer composition, demonstrating the gradient character of the copolymers, and the microstructure were analyzed. The experimental data agreed well with data calculated with the Mayo–Lewis terminal model and Bernoullian statistics, with monomer reactivity ratios of 2.58 ± 0.37 and 0.51 ± 0.05 for A and B, respectively, an isotacticity parameter for A of 0.24, and a coisotacticity parameter of 0.33. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5304–5315, 2006     

Synthesis of poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) by the competitive single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization in water

The synthesis of a block copolymer poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) is reported. This new material was synthesized by single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization (SET‐DTLRP) in two steps. First, a bifunctional macroinitiator of α,ω‐di(iodo)poly (butyl acrylate) [α,ω‐di(iodo)PBA] was synthesized by SET‐DTLRP in water at 25 °C. The macroinitiator was further reinitiated by SET‐DTLRP, leading to the formation of the desired product. This ABA block copolymer was synthesized with high initiator efficiency. The kinetics of the copolymerization reaction was studied for two PBA macroinitiators with number–average molecular weight of 10 k and 20 k. The relationship between the conversion and the number–average molecular weight was found to be linear. The dynamic mechanical thermal analysis suggests just one phase, indicating that copolymer behaves as a single material with no phase separation. This methodology provides the access to several block copolymers and other complex architectures that result from combinations of thermoplastics (PVC) and elastomers (PBA). From industrial standpoint, this process is attractive, because of easy experimental setup and the environmental friendly reaction medium. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3001–3008, 2006     

Single electron transfer–degenerative chain transfer living radical polymerization of N‐butyl acrylate catalyzed by Na2S2O4 in water media

Living radical polymerization of n‐butyl acrylate was achieved by single electron transfer/degenerative‐chain transfer mediated living radical polymerization in water catalyzed by sodium dithionate. The plots of number–average molecular weight versus conversion and ln[M]₀/[M] versus time are linear, indicating a controlled polymerization. This methodology leads to the preparation of α,ω‐di(iodo) poly (butyl acrylate) (α,ω‐di(iodo)PBA) macroinitiators. The influence of polymerization degree ([monomer]/[initiator]), amount of catalyst, concentration of suspending agents and temperature were studied. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right‐angle light scattering (RALLS), a differential viscometer (DV), and refractive index (RI). The methodology studied in this work represents a possible route to prepare well‐tailored macromolecules made of butyl acrylate in an environmental friendly reaction medium. Moreover, such materials can be subsequently functionalized leading to the formation of different block copolymers of composition ABA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2809–2825, 2006