Thorium,uranium and plutonium isotopes in the Arkansas River

Radiochemical measurements of the concentrations of thorium, uranium and plutonium isotopes were carried out for the samples of Arkansas River collected at six locations in the states of Colorado and Oklahoma. The uranium to thorium ratios in the river samples were found to be highly variable and generally much greater than the ratios found in soils and in rainwater. An attempt has been made to determine the apparent²³⁰Th ages (or the times which elapsed since the last major disruption of the radioactive equilibria) from the observed²³⁰Th/²³²Th and²³⁴U/²³²Th ratios in the water samples.     

Theoretical study on solvation effects in chemical reactions: A vibrational coupling model

A vibrational coupling model to treat the solvation effects in chemical reaction rate calculations is proposed and applied to the intramolecular hydrogen transfer reaction CH₃O· → ·CH₂OH in the condensed phase. The effect of solvation is taken into account in two ways: (1) the solvent effect on the activation energy of the reaction is simulated by including 39 surrounding water molecules, represented by fractional charges at the assumed atomic positions, in the potential energy surface calculation; and (2) the vibrational couplings between the 10 nearest solvent molecules and the molecules constituting the reaction system are explicitly included in a vibrational frequency calculation. RRKM theory with Miller's tunneling correction included is employed to calculate the rate constants. The effect of solvation causes a significant change in the chemical reaction rate, mainly through a lowering of the activation energy. The vibrational coupling causes a slight increase of the rate constant in the tunneling region by perturbing the vibrational frequencies of the reactant and transition states, which appear in the rate-constant expression, but has little effect at higher temperatures.     

Anion-exchange behaviour of a number of metal ions on DEAE-cellulose in hydrobromic and hydriodic acid media

Summary The adsorption behaviour of 48 metal ions on DEAE-cellulose layers has been investigated in aqueous hydrobromic and hydriodic acid media. R_F values are given as a function of the hydrobromic and hydriodic acid concentration over the ranges 0.01–6 mol dm^–3 and 0.01–3 mol dm^–3, respectively, and are compared with those obtained with Avicel SF. R_F spectra are comparatively simple in both media, reflecting the strong affinity of the bromide and iodide ions to the DEAE-cellulose phase. Pd, Pt, Re, Au and Hg are distributed chromatographically in either system, while most other metal ions exhibit rather extreme R_F values of near unity or zero. Therefore, the selectivity of the systems is particularly high for Pd, Pt, Re, Au and Hg, providing the possibility of their excellent selective separations.     

Flow analysis of silicate rocks for zirconium

A flow analysis system involving the on-line configuration of an anion-exchange column has been examined to enrich and determine trace concentrations of zirconium of several ppm to hundred ppm levels in silicate rocks and minerals. About 100 mg of sample is decomposed by fusion with a mixture of boric acid and lithium carbonate and taken up with 1M hydrochloric acid to a total of 100 ml. Depending upon the concentration of zirconium, either a 1- or 4-ml aliquot is introduced into an aqueous carrier stream, merged with sulphuric acid and passed through a small volume anion-exchange column. The enriched zirconium is then back eluted with hydrochloric acid, colour-developed with Arsenazo III, and detected spectrophotometrically at 665 nm.     

Synthetic studies on glycosphingolipids from protostomia phyla: synthesis of a glycosphingolipid analogue from the parasite Spirometra erinacei

Novel neutral glycosphingolipids isolated from the plerocercoids of a tapeworm, Spirometra erinacei, may be expected to be involved in host-parasite interactions. We have synthesized this glycosphingolipid analogue containing 2-branched fatty alkyl residue in place of ceramide. Glycosylation of nonreducing-end trisaccharide derivative 15 with the reducing-end disaccharide derivative 17 in the presence of trimethylsilyl triflate (TMSOTf) gave the desired oligosaccharide derivative in good yield. The fully per-O-acylated 2-(trimethylsilyl)ethyl glycoside 19 was converted to glycosylimidate 20, which was condensed with 2-(tetradecyl)hexadecanol and subsequently deacylated to give the target glycosphingolipid analogue 22.     

Plutonium-244 fission xenon in carbonaceous inclusions of primitive meteorites

A total of 13 samples of diamond separates studied so far, all contain excess ²⁴⁴Pu fission xenon. On the other hand, none of the SiC separates contains excess ²⁴⁴Pu fission xenon, while 5 out of 10 samples of graphite separates studied so far contain excess ²⁴⁴Pu fission xenon.     

Plutonium-244 dating

Re-calculation of the²⁴⁴Pu ages of lunar rocks 10057 and 12013 indicates that, while the former started to retain its xenon (4,189 _?74 ⁺⁴⁵ ) million years ago, the latter was formed at a much later time, after the extinct nuclide²⁴⁴Pu had essentially decayed away.     

Anisotropic contributions in the ligand polarization model for the f-f transition probabilities of Eu(III) complexes

The intensities of the ΔM = ± 1 component of the ⁷f_o→ ⁵D₂ transition in D₃ complexes containing the [ EuO₉] cluster, and of other d-d or f-f transitions in D₃ complexes with the yz- and xz-components of the electric quadrupole as the leading moment, are found to be dependent upon the polarizability anisotropy of the ligands. The expectation is supported by determinations of the single-crystal absorption intensities of Na₃ [Eu(diglycollate)₃]·2NaClO₄·6H₂O and [Eu(H₂O)₉] (C₂H₅SO₄)₃.     

Alternating copolymer of thiophene andN‐(phenylethynyl)pyrrole. New π‐conjugated alternating five‐membered ring copolymer and its packing structure

An alternating copolymer, Copoly‐1 , of thiophene and N‐(phenylethynyl)pyrrole was prepared by palladium‐catalyzed polycondensation. Powder X‐ray diffraction (XRD) analysis indicated that Copoly‐1 formed a stacked packing structure with doubly‐running polymer main chains. Optical data support the molecular and packing structures of Copoly‐1 . © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2219–2224, 2005