Simulataneous substoichiometric determination of europium and terbium with diethylenetriaminepentaacetic acid and 2-thenoyltrifluoroacetone

The simultaneous substoichiometric separation of europium and terbium is presented and its application to the determination of these elements with DTPA and HTTA is developed. Experimental results for the simultaneous substoichiometric separation are in good agreement with the theoretical results introduced by the principle. Europium and terbium in orchard leaves are determined by simultaneous substoichiometric neutron activation. The analytical values are 23±1.1 ppb for europium, and 17±1.2 ppb for terbium.     

Mechanistic insights in charge-transfer-induced luminescence of 1,2-dioxetanones with a substituent of low oxidation potential

We have investigated the decomposition pathway of dioxetanones 1c with a phenoxide anion group by the B3LYP/6-31+G(d) method together with the second-order multireference M?ller-Plesset perturbation (MRMP) theory and propose charge-transfer-induced luminescence (CTIL) with polarization-induced branching excitation processes. In the gas phase, the thermal decomposition of 1c occurs by an asynchronous two-stage pathway without a discrete intermediate; that is, the initial O-O bond breaking to generate a charge-transfer (CT) diradical species is immediately followed by the subsequent C-C bond breaking with simultaneous back CT, which is responsible for the surface crossing at the avoided crossing. The activation energy is dramatically reduced from 19.4 to 3.8 kcal mol(-)(1) by the deprotonation of phenol meta-1d to its anion meta-1c, showing an important role of the endothermic CT. The odd/even selection rule for the chemiluminescence efficiency can be explained by the orbital interaction for the back CT between the carbonyl pi orbital and either a HOMO or a LUMO of the generated light emitters. To examine the accessibility of the chemically initiated electron exchange luminescence (CIEEL) route, we considered the solvent effects on the free-energy change of meta-1c by using continuum solvent models. The bending vibration mode of the CO(2) fragment is specifically considered. Borderline features emerges from the solution-phase CT reaction of meta-1c, which depends on the solvent polarity: one is a nonadiabatic or adiabatic back CT process (polarization-induced concerted CTIL), and the other is a radical dissociation, i.e., complete one-electron-transfer process (CIEEL).     

Determination of uranium by neutron activation analysis using substoichiometric separation

Three analytical methods for uranium by neutron activation are described. The methods are based on the substoichiometric separation of barium or lanthanum, which are the fission products of uranium-235 by neutron irradiation. Uranium contents in high purity materials were determined by the methods, which were found to be useful for the determination of a trace amounts of uranium.     

Stereoselective synthesis of Nuphar quinolizidine alkaloid, (−)-deoxynupharidine

A stereoselective synthetic route to Nuphar quinolizidine alkaloid, (−)-deoxynupharidine, was established by employing reductive carbon-nitrogen bond cleavage, followed by simultaneous recyclization of a proline derivative with samarium diiodide, and an intramolecular ring-closing metathesis, as the key steps.     

Synthesis of dihydroxamic acid chelating polymers and the adsorptive property for uranium in sea water

Preparation of new chelating polymers bearing dihydroxamic acid groups and the adsorptive ability for uranium in sea water are described. Chloromethylated polystyrene crosslinked with divinylbenzene was treated with diethyl malonate in N, N-dimethylformamide to give the polymer having diethyl malonate groups. This polymer was then treated with hydroxylamine in methanol to afford the dihydroxamic acid polymer. The presence of hydroxamic acid groups was confirmed by the appearance of IR absorption band at 1680 cm^?1. The dihydroxamic acid polymer contained carboxylic acid groups as well as hydroxamic acid ones, and the contents of carboxylic acid and hydroxamic acid groups were estimated from elemental analysis to be 2–3 and 2–4 mmol/g, respectively. The polymer showed the adsorptive ability of 40 μg-U/g in 8 days for uranium in sea water. In addition, the polymer showed the selective adsorptivity for iron, nickel, copper, and zinc as well as uranium. The macroreticular-type polymer showed much higher adsorption rate for uranium in sea water than the gel-type ones did, suggesting that the rate depends on the diffusion of the uranium in the polymer support.     

Studies toward the total synthesis of scyphostatin: first entry to the highly functionalized cyclohexenone segment

The cyclohexenone segment 2 of scyphostatin (1), a potent inhibitor of neutral sphingomyelinase, was synthesized in an enantioselective manner starting from the bromo ether 5 and D-serinal derivative 3. The synthetic method features a coupling reaction of 5 with 3 to construct the asymmetric quaternary carbon center and a stereospecific epoxide ring formation as the key steps.     

Formal total synthesis of ottelione using iridium-catalyzed oxidative desymmetrization

A catalytic asymmetric synthesis of a key intermediate for ottelione has been achieved using oxidative desymmetrization as the critical step. This oxidative desymmetrization was efficiently promoted by an iridium diamine complex to give the desired hydroxy ketone in >99% ee and 60% yield.     

Asymptotic expansion of the one-loop approximation of the Chern–Simons integral in an abstract Wiener space setting

In an abstract Wiener space setting, we construct a rigorous mathematical model of the one-loop approximation of the perturbative Chern–Simons integral, and derive its explicit asymptotic expansion for stochastic Wilson lines.