John C. Stewart

The average electrostatic potential near a nucleus immersed in a plasma is evaluated using a finitetemperature Thomas-Fermi model. The part of this potential directly attributable to the presence of the plasma is isolated and is used to evaluate the reduction in ionization potential for a wide range of parameters. A simple analytic solution, exhibiting Debye-Hiickel and ion-sphere limits, is also obtained and is used as an interpolatory device.

Carbon monoxide (CO) is in principle an excellent resource from which to produce industrial hydrocarbon feedstocks as alternatives to crude oil; however, CO has proven remarkably resistant to selective homologation, and the few complexes that can effect this transformation cannot be recycled because liberation of the homologated product destroys the complexes or they are substitutionally inert. Here, we show that under mild conditions a simple triamidoamine uranium(III) complex can reductively homologate CO and be recycled for reuse. Following treatment with organosilyl halides, bis(organosiloxy)acetylenes, which readily convert to furanones, are produced, and this was confirmed by the use of isotopically (13)C-labeled CO. The precursor to the triamido uranium(III) complex is formed concomitantly. These findings establish that, under appropriate conditions, uranium(III) can mediate a complete synthetic cycle for the homologation of CO to higher derivatives. This work may prove useful in spurring wider efforts in CO homologation, and the simplicity of this system suggests that catalytic CO functionalization may soon be within reach.

A number of authors have observed, by using light scattering from a laser beam, contamination particles suspended in an rf process plasma. The region of space occupied by the particles appears finite, e.g., a ring; there is experimental evidence that the particles are negatively charged. We show, by using a tuned Langmuir probe, that the trap is electrostatic in nature. The volume of a trap is as much as 5 V larger in electrostatic potential than the surrounding plasma. This means that the volume of the trap is positively charged with the electric field being directed outward from the trap. Thus, negatively charged particles will flow into it. The electrostatic potential rises so rapidly at a trap boundary that a double layer may exist there. Finally, the plasma-sheath interface is found to follow the topographic contour of the rf electrode surface.

Halogen bonding (R-X···Y) is a qualitative analogue of hydrogen bonding that may prove useful in the rational design of artificial proteins and nucleotides. We explore halogen-bonded DNA base pairs containing modified guanine, cytosine, adenine and thymine nucleosides. The structures and stabilities of the halogenated systems are compared to the normal hydrogen bonded base pairs. In most cases, energetically stable, coplanar structures are identified. In the most favorable cases, halogenated base pair stabilities are within 2 kcal mol(-1) of the hydrogen bonded analogues. Among the halogens X = Cl, Br, and I, bromine is best suited for inclusion in these biological systems because it possesses the best combination of polarizability and steric suitability. We find that the most stable structures result from a single substitution of a hydrogen bond for a halogen bond in dA:dT and dG:dC base pairs, which allows 1 or 2 hydrogen bonds, respectively, to complement the halogen bond.