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Selected AbstractsPreparation of Arylphosphonates by Palladium(0)-Catalyzed Cross-Coupling in the Presence of Acetate Additives: Synthetic and Mechanistic StudiesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 18 2009Marcin Kalek Abstract An efficient protocol for the synthesis of arylphosphonate diesters via a palladium-catalyzed cross-coupling of H-phosphonate diesters with aryl electrophiles, promoted by acetate ions, was developed. A significant shortening of the cross-coupling time in the presence of the added acetate ions was achieved for bidentate and monodentate supporting ligands, and for different aryl electrophiles (iodo, bromo and triflate derivatives). The reaction conditions were optimized in terms of amount of the catalyst, supporting ligands, and source of the acetate ion used. Various arylphosphonates, including those of potential biological significance, were synthesized using this newly developed protocol. Some mechanistic aspects of the investigated reactions are also discussed. [source] Stability of poly(3,4-ethylene dioxythiophene) materials intended for implants,JOURNAL OF BIOMEDICAL MATERIALS RESEARCH, Issue 2 2010Elin M. Thaning Abstract This study presents experiments designed to study the stability of the conducting polymer poly(3,4-ethylene dioxythiophene) (PEDOT), under simulated physiological conditions using phosphate-buffered saline (PBS) and hydrogen peroxide (H2O2) (0.01M) at 37°C over a 5- to 6-week period. Voltage pulsing in PBS was used as an additional test environment. The influence of switching the counter ion used in electropolymerization from polystyrene sulphonate (PSS) to heparin was investigated. Absorbance spectroscopy and cyclic voltammetry were used to evaluate the material properties. Most of the samples in H2O2 lost both electroactivity and optical absorbance within the study period, but PEDOT:PSS was found slightly more stable than PEDOT:heparin. Polymers were relatively stable in PBS throughout the study period, with around 80% of electroactivity remaining after 5 weeks, disregarding delamination, which was a significant problem especially for polymer on indium tin oxide substrates. Voltage pulsing in PBS did not increase degradation. The counter ion influenced the time course of degradation in oxidizing agents. © 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 2010 [source] Permselective and Preconcentration Properties of a Surfactant-Intercalated Clay Modified ElectrodeELECTROANALYSIS, Issue 22 2006E. Ngameni Abstract This work is focused on the voltammetric examination of the ion exchange properties of a smectite type clay, before and after its modification by the replacement of its native interlamellar cations (Na+, K+, Ca2+) by hexadecyltrimethylammonium cations (HDTMA+). The raw clay and its organically modified form were first characterized by X-ray diffraction (XRD) and N2 adsorption,desorption isotherms (BET method) that confirmed the modification via an intercalation process. These materials were subsequently coated onto glassy carbon surfaces, and the resulting modified electrodes were evaluated for the uptake of [Ru(NH3)6]3+ and [Fe(CN)6]3, ions used as redox probes. Some experimental parameters affecting the incorporation of the probes within the film, including the ionic strength, the surfactant loading and the solution pH are thoroughly examined, in order to highlight the mechanism of the process. The possibility of using the surfactant-intercalated clay modified electrode as an electrochemical sensor for [Fe(CN)6]3, is also evaluated. [source] Shape-Controlled Synthesis of Pd Nanocrystals in Aqueous SolutionsADVANCED FUNCTIONAL MATERIALS, Issue 2 2009Byungkwon Lim Abstract This article provides an overview of recent developments regarding synthesis of Pd nanocrystals with well-controlled shapes in aqueous solutions. In a solution-phase synthesis, the final shape taken by a nanocrystal is determined by the twin structures of seeds and the growth rates of different crystallographic facets. Here, the maneuvering of these factors in an aqueous system to achieve shape control for Pd nanocrystals is discussed. L -ascorbic acid, citric acid, and poly(vinyl pyrrolidone) are tested for manipulating the reduction kinetics, with citric acid and Br, ions used as capping agents to selectively promote the formation of {111} and {100} facets, respectively. The distribution of single-crystal versus multiple-twinned seeds can be further manipulated by employing or blocking oxidative etching. The shapes obtained for the Pd nanocrystals include truncated octahedron, icosahedron, octahedron, decahedron, hexagonal and triangular plates, rectangular bar, and cube. The ability to control the shape of Pd nanocrystals provides a great opportunity to systematically investigate their catalytic, electrical, and plasmonic properties. [source] The properties of the Mn, Ni and Pb transport operating at plasma membranes of cucumber rootsPHYSIOLOGIA PLANTARUM, Issue 3 2007Magdalena Migocka To avoid metal toxicity, plants have developed mechanisms including efflux of metal ions from cells and their sequestration into cellular compartments. In this report, we present evidence for the role of plasma membrane efflux systems in metal tolerance of cucumber roots. We have identified the plasma membrane-transport system participating in Cd, Pb, Mn and Ni efflux from the cytosol. Kinetic characterization of this proton-coupled transport system revealed that it is saturable and has a different affinity for each of the metal ions used (with Km 5, 7.5 and 0.1 mM for Mn, Ni and Pb, respectively). Treatment of cucumber roots with 100 ,M Cd prior to the transport measurements caused a great increase (over 250%) in Cd antiport activity in plasmalemma vesicles. After decreasing the metal concentration to 50 ,M we still observed a large increase (over 150%) of this activity in comparison with the control. Moreover, the addition of 50 ,M Cd to the external solution stimulated not only Cd antiport in the plasmalemma vesicles but also the antiport of other metals used in the experiments. Treatment of cucumber roots with 50 ,M Ni revealed a similar effect: the antiport activity of Cd, Mn, Ni and Pb was stimulated, although to a lesser extent in comparison with stimulation by Cd. The data indicate that the root plasma membrane antiporter system is stimulated by the exogenous presence of heavy metals. [source] The quantification of carbon dioxide in humid air and exhaled breath by selected ion flow tube mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 10 2009David Smith The reactions of carbon dioxide, CO2, with the precursor ions used for selected ion flow tube mass spectrometry, SIFT-MS, analyses, viz. H3O+, NO+ and O, are so slow that the presence of CO2 in exhaled breath has, until recently, not had to be accounted for in SIFT-MS analyses of breath. This has, however, to be accounted for in the analysis of acetaldehyde in breath, because an overlap occurs of the monohydrate of protonated acetaldehyde and the weakly bound adduct ion, H3O+CO2, formed by the slow association reaction of the precursor ion H3O+ with CO2 molecules. The understanding of the kinetics of formation and the loss rates of the relevant ions gained from experimentation using the new generation of more sensitive SIFT-MS instruments now allows accurate quantification of CO2 in breath using the level of the H3O+CO2 adduct ion. However, this is complicated by the rapid reaction of H3O+CO2 with water vapour molecules, H2O, that are in abundance in exhaled breath. Thus, a study has been carried out of the formation of this adduct ion by the slow three-body association reaction of H3O+ with CO2 and its rapid loss in the two-body reaction with H2O molecules. It is seen that the signal level of the H3O+CO2 adduct ion is sensitively dependent on the humidity (H2O concentration) of the sample to be analysed and a functional form of this dependence has been obtained. This has resulted in an appropriate extension of the SIFT-MS software and kinetics library that allows accurate measurement of CO2 levels in air samples, ranging from very low percentage levels (0.03% typical of tropospheric air) to the 6% level that is about the upper limit in exhaled breath. Thus, the level of CO2 can be traced through single time exhalation cycles along with that of water vapour, also close to the 6% level, and of trace gas metabolites that are present at only a few parts-per-billion. This has added a further dimension to the analysis of major and trace compounds in breath using SIFT-MS. Copyright © 2009 John Wiley & Sons, Ltd. [source] |