The first experimental observation of electronic transitions in C2+ and C2D+

High-resolution translational energy spectroscopy (up to 0.1 eV) has been carried out on 8 kV of C₂⁺ and C₂D⁺. The spetra obtained with C₂⁺ formed by different methods show considerable differences which are attributed to the formation of different spin states of the ion. Tentative assignments for the observed transitions have been made including one corresponding to excitation of the ⁴∑_g^? —X ⁴∑_g^? system, which may be useful as a probe of interstellar C₂⁺. Two broad transitions have been seen in the translational energy spectrum of C₂D⁺ which are in reasonable agreement with existing theoretical calculations. Tentative assignments are proposed for these transitions.     

Notes on the dynamics of pension funding

The authors follow up some previous work on the dynamics of pension funding by three notes. The first of these concerns contribution rates consisting of the normal cost plus a generalized amortization method for unfunded supplemental present value (actuarial accrued liability). The second note examines aggregate cost funding for active members when there exist consistent difference between the assumed and the actual rates of interest and of growth. The third note explores the operation of a variable annuity system in the context of our general model for pension funding dynamics.     

Surface and aggregation behavior of aqueous solutions of Ru(II) metallosurfactants. 3. Effect of chain number and orientation on the structure of adsorbed films of [Ru(bipy)2(bipy')]Cl2 complexes

The surface behavior of a range of surfactant [Ru(bipy)(2)(p,p'-dialkyl-2,2'-bipy)]Cl(2) complexes, which we express as Ru(q)(p)C(n) where n is the alkyl chain length, p refers to the substitution position on the bipyridine ligand (=4 or 5), and q (=1 or 2) is the number of substituted alkyl chains, has been examined using neutron reflectometry. The adsorption of the single-chain Ru(1)(4)C(19) and Ru(1)(5)C(19) surfactants is strongly time-dependent, taking in excess of 10 h to form an equilibrium film. It is suggested that the slow adsorption rate is related to the alkyl chain length rather than the low monomer concentration present in the solutions. At concentrations below the critical micelle concentration (cmc) of Ru(1)(4)C(19), the film of Ru(1)(5)C(19) is denser than that of Ru(1)(4)C(19) at comparable concentration, consistent with the mass densities of the bulk solids, whereas at concentrations close to and greater than this cmc the converse pertains. Close to the cmc, the adsorbed films possess an average area per molecule significantly less than the nominal headgroup area of the surfactants (approximately 30 angstroms(2) compared with approximately 100 angstroms(2)). This fact together with consideration of the thickness and density of the adsorbed films leads to the conjecture that surface aggregates may be the adsorbing units. The adsorption of the double-chain surfactant Ru(1)(p)C(19), in contrast to the behavior of the Ru(1)(p)C(19) surfactants, is weak and independent of time. This behavior is attributed to the alkyl chain orientation. The adsorption behavior of a racemic mixture of the Delta and Lambda isomers of Ru(2)(4)C(19) has been compared with that of the Delta isomer. It is found that the film of racemic material is more closely packed than that of the resolved complex.     

Dioxygenase-catalysed oxidation of disubstituted benzene substrates: benzylic monohydroxylation versus aryl cis-dihydroxylation and the meta effect

Biotransformations of a series of ortho-, meta- and para-substituted ethylbenzene and propylbenzene substrates have been carried out, using Pseudomonas putida UV4, a source of toluene dioxygenase (TDO). The ortho- and para-substituted alkylbenzene substrates yielded, exclusively, the corresponding enantiopure cis-dihydrodiols of the same absolute configuration. However, the meta isomers, generally, gave benzylic alcohol bioproducts, in addition to the cis-dihydrodiols (the meta effect). The benzylic alcohols were of identical (R) absolute configuration but enantiomeric excess values were variable. The similar (2R) absolute configurations of the cis-dihydrodiols are consistent with both the ethyl and propyl groups having dominant stereodirecting effects over the other substituents. The model used earlier, to predict the regio- and stereo-chemistry of cis-dihydrodiol bioproducts derived from substituted benzene substrates has been refined, to take account of non-symmetric substituents like ethyl or propyl groups. The formation of benzylic hydroxylation products, from meta-substituted benzene substrates, without further cis-dihydroxylation to yield triols provides a further example of the meta effect during toluene dioxygenase-catalysed oxidations.     

Synthesis of a beta-(1-->3)-D-rhamnotetraose by a one-pot, multiple radical fragmentation

A naturally occurring beta-(1-->3)-D-rhamnotetraose has been constructed under conditions of sequential beta-selective mannosylation controlled by the 4,6-O-[1-cyano-2-(2-iodophenyl)-ethylidene] protecting group. The route is concise, proceeding through a late-stage radical deoxygenation that successfully uncovers all four deoxy subunits at once.     

Theory of laser acceleration of light-ion beams from interaction of ultrahigh-intensity lasers with layered targets

Experiments at the LANL Trident facility demonstrated the production of monoenergetic ion beams from the interaction of an ultraintense laser with a target comprising a heavy ion substrate and thin layer of light ions. An analytic model is obtained that predicts how the mean energy and quality of monoenergetic ion beams and the energy of substrate ions vary with substrate material and light-ion layer composition and thickness. Dimensionless parameters controlling the dynamics are derived and the model is validated with particle-in-cell simulations and experimental data.