Novel fixed‐site–carrier polyvinylamine membrane for carbon dioxide capture

Fixed‐site–carrier membranes were prepared for the facilitated transport of CO₂ by casting polyvinylamine (PVAm) on various supports, such as poly(ether sulfone) (PES), polyacrylonitrile (PAN), cellulose acetate (CA), and polysulfone (PSO). The cast PVAm on the support was crosslinked by various methods with glutaraldehyde, hydrochloric acid, sulfuric acid, and ammonium fluoride. Among the membranes tested, the PVAm cast on polysulfone and crosslinked by ammonium fluoride showed the highest selectivity of CO₂ over CH₄ (>1000). The permeance of CO₂ was then measured to be 0.014 m³ (STP)/(m² bar h) for a 20 μm thick membrane. The effect of the molecular weight of PVAm and feed pressure on the permeance was also investigated. The selectivity increased remarkably with increasing molecular weight and decreased slightly with increased pressure in the range of 1 to 4 bar. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4326–4336, 2004     

Analyse systemati oue d'elements en traces dans l'or metalli oue par activation neutroni oue

Résumé Une méthode d'analyse des impuretés dans l'or métallique par activation neutronique, a été mise au point. Après irradiation de 15 heures dans un flux de 2·10¹⁴ n·cm⁻²·sec⁻¹, l'échantillon d'or est traité en cellule blindée. La matrice est séparée des impuretés à analyser par des méthodes électrolytiques. Les impuretés sont généralement séparées en 3 fractions qui sont mesurées par spectrométrie γ. Le traitement des informations est effectué sur ordinateur IBM 360/91 moyennant un programme écrit au laboratoire. 29 éléments sont détectables par cette méthode.     

Determination quantitative des impuretes des graphites nucleaires par les methodes de radioactivation analyse systematique

Impurities contained in nuclear graphites have been determined so far individually. A method of systematic analysis is described which permits to determine about twenty impurities in one sample, such as the following elements: Ag, Se, Hg, Sb, Cu, Fe, Ga, Co, Cd, Zn, In, Zr, Cr, Sc, Ba, Ca, Na, K, Rb, and Cs. Brief mention is made of methods used for the determination of all rare earth metals, Si, S and P, as well as the elements which can be determined without chemical separation, such as Cl, Mn, V.

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Determination quantitative des impuretes des graphites nucleaires par les methodes de radioactivation analyse systematique

     

Chromatographic analysis of hydrocarbons in marine sediments and seawater.

The low concentration of hydrocarbons anticipated in pollution baseline studies necessitates the development of analytical techniques sensitive at the sub-microgram per kilogram concentration level. The method of analysis developed in this laboratory involves dynamic headspace sampling for volatile hydrocarbon components of the sample, followed by coupled-column liquid chromatography for the non-volatile components. These techniques require minimal sample handling, reducing the risk of sample component loss and/or sample contamination. Volatile sample components are separated from the matrix in a closed system and concentrated on a TENAX-GC packed pre-column, free from large amounts of solvent and ready for GC/GC-MS analysis. Non-volatile compounds, such as the benzpyrenes, may be extracted from large volumes of water and concentrated on a Bondapak C18 packed pre-column for coupled-column liquid chromatographic separation and analysis. Results of the application of these techniques to the analysis of samples from sites of known low level hydrocarbon contamination are presented and discussed.     

A simple convenient synthesis of trans-1,2,3,4,4a,5,6,10b-octahydrophenanthridines

trans-1,2,3,4,4a,5,6,10b-Octahydrophenanthridine, the 9-methoxy analog, and 5-methyl derivatives ( 6a,6b ) of each have been synthesized from trans-phenylcyclohexylamines ( 2a,2b ) and ethyl chloroformate followed by cyclization and reduction or by cyclization, N-methylation and reduction. The oximes ( la,1b ) of 2-phenylcyclohexanone and the m-methoxy relative, a mixture of the syn and anti isomers, were reduced to 2a and 2b with sodium and ethanol. Hydrogenation (platinum oxide-acetic acid) of 1a gave in addition to 2a , a small yield of 2-cyclohexylcyclohexyl-amine. Similar hydrogenation of 1b gave only this fully reduced compound.     

Zdanovskii’s Rule and Isopiestic Measurements Applied to Synthetic Bayer Liquors

Isopiestic measurements of mixed electrolyte solutions involving sodium hydroxide and other components of Bayer liquors were performed at 50?°C and 100?°C. Most of the systems studied obey Zdanovskii’s rule exactly or very closely. However, those with sodium chloride as one of their components show deviations from Zdanovskii’s rule, which are well predicted by our thermodynamic modelling software based on Pitzer’s equations.     

A modified method for the determination of methylmercury by gas chromatography

A simple modification of the West?? extraction procedure for methylmercury and its determination by gas chromatography (GC) is presented. The cysteine clean-up step has been modified, with use of cysteine-impregnated paper instead of cysteine solution. Methylmercury bromide is extracted from the sample into toluene and is selectively adsorbed on the cysteine paper. Interfering compounds are washed from the paper with toluene. The isolated methylmercury is set free with sulphuric acid containing bromide, extracted into benzene and determined by GC. The modification of the extraction procedure results in good recovery and reproducibility for various biological and environmental samples, good sensitivity with a detection limit of 0.1 ng/g, avoidance of difficulties arising from emulsion formation, cleaner chromatograms, and faster analysis. It is particularly suitable for determination of low levels of MeHg.     

Selenium redox cycling in the protective effects of organoselenides against oxidant-induced DNA damage

The biological role of selenium is a subject of intense current interest, and the antioxidant activity of selenoenzymes is now known to be dependent upon redox cycling of selenium within their active sites. Exogenously supplied or metabolically generated organoselenium compounds, capable of propagating a selenium redox cycle, might therefore supplement natural cellular defenses against the oxidizing agents generated during metabolism. We now report evidence that selenium redox cycling can enhance the protective effects of organoselenium compounds against oxidant-induced DNA damage. Phenylaminoethyl selenides were found to protect plasmid DNA from peroxynitrite-mediated damage by scavenging this powerful cellular oxidant and forming phenylaminoethyl selenoxides as the sole selenium-containing products. The redox properties of these organoselenoxide compounds were investigated, and the first redox potentials of selenoxides in the literature are reported here. Rate constants were determined for the reactions of the selenoxides with cellular reductants such as glutathione (GSH). These kinetic data were then used in a MatLab simulation, which showed the feasibility of selenium redox cycling by GSH in the presence of the cellular oxidant, peroxynitrite. Experiments were then carried out in which peroxynitrite-mediated plasmid DNA nick formation in the presence or absence of organoselenium compounds and GSH was monitored. The results demonstrate that GSH-mediated redox cycling of selenium enhances the protective effects of phenylaminoethyl selenides against peroxynitrite-induced DNA damage.     

The first structural and spectroscopic characterization of a neptunyl polyoxometalate complex

The reaction between PW9O349- and NpO2+ has yielded the first structurally characterized neptunyl(V) polyoxometalate complex, [Na2(NpO2)2(A-PW9O34)2]14-. This complex is isostructural with the uranyl(VI) analogue, and there is also spectroscopic evidence for its existence in solution. The complex is readily extracted into toluene, and this may have significance in the sequestering and/or separation of the neptunyl ion in terms of nuclear waste management.     

Matrix-dependent instability of selenium(IV) stored in teflon containers

Solutions of selenium(IV) standards with different acid matrices were stored in containers constructed of boosilicate glass, conventional polyethylene, and fluorinated ethylenepropylene (teflon FEP). After 50 days of storage in FEP, there were highly significant losses of Se(IV) from standards in either 5% HCl/5% H₂SO₄, or 5% H₂SO₄. Increasing the hydrochloric acid concentration, e.g., 15% HCl/5% H₂SO₄, greatly reduced this loss. Addition of selenium-75 (selenate-free) indicated that the losses did not result from physical adsorption onto container surfaces. It is shown that the losses were caused by oxidation of Se(IV) to Se(VI).