Theoretical study of [F−; e+] and [CN−; e+]

Ab initio calculations are presented for the [F^?; e⁺] and [CN^?; e⁺] complexes. Positron affinities of 4.99 and 3.79 eV are obtained for F^? and CN^?, respectively. The excitation energies to the low-lying excited states of the positron complexes are also calculated.     

Simultaneous determination of trace concentrations of saturated and α,β-unsaturated carbonyl compounds in organic systems

A method for the simultaneous determination of trace concentrations of saturated and α,β-unsaturated carbonyl compounds in complex systems is presented. Carbonyl as the alkaline 2,4-dinitrophenylhydrazone is determined spectrophotometrically at 2 selected wavelengths of 480 and 426 nm. The apparent total carbonyl concentration is obtained from prepared calibration curves at the selected wavelengths based on known concentrations of n-heptaldehyde. From the observed relative response of known concentrations of n-heptaldehyde and 2-ethyl-2-hexenal, the true concentration for saturated and α,β-unsaturated carbonyl is obtained by a simple calculation. The method has been used extensively for alcohol systems ranging up to tetracontanol but is equally useful for hydrocarbons, aromatic oxygenates and hydrocarbons, petroleum distillates and kerosenes, organic acids and esters, and some ethers.     

Mechanisms of phosphate transfer on the purine salvage pathway

Abstract

α-D-Ribofuranosyl-1,2-cyclic monophosphate and 5-phospho-α-D-ribofuranosy1-1, 2-cyclic monophosphate were synthesized in good yields. The five-membered ring cyclic phosphates have ³¹p chemical shifts similar to those found for such structures, presumably reflecting the smaller O-P-O bond angle, compared to that in six-membered ring phosphates. The rate of OH^? catalyzed ring opening was similar to that reported for ethylene phosphate, indicating relief of ring strain during hydrolysis. α-D-Ribofuranosyl-1, 2-cyclic monophosphate was found to irreversibly inactivate purine nucleoside phosphorylase (EC 2.4.2.1) at its catalytic center.     

Palladium‐Catalyzed Direct CH Functionalization of Benzoquinone

A direct Pd‐catalyzed C? H functionalization of benzoquinone (BQ) can be controlled to give either mono‐ or disubstituted BQ, including the installation of two different groups in a one‐pot procedure. BQ can now be directly functionalized with aryl, heteroaryl, cycloalkyl, and cycloalkene groups and, moreover, the reaction is conducted in environmentally benign water or acetone as solvents.     

Exact Formula for Currents in Strongly Pumped Diffusive Systems

We analyze a generic model of mesoscopic machines driven by the nonadiabatic variation of external parameters. We derive a formula for the probability current; as a consequence we obtain a no-pumping theorem for cyclic processes satisfying detailed balance and demonstrate that the rectification of current requires broken spatial symmetry.     

Halophilic reactions of a stable silylene with chloro and bromocarbons

A number of disilanes have been synthesized from a stable silylene, 1 (N,N'-di-tert-butyl-1,3-diaza-2-silacyclopent-4-en-2-ylidene), and a variety of halocarbons. It is proposed that disilane formation is a result of an initial halophilic interaction between the silylene and halocarbon. Formation of disilanes from 1 and CCl4, 2a, CHCl3, 2b, CH2Cl2, 2c, benzyl chloride, 2d, and bromobenzene, 5, are described here. An X-ray crystal structure of 2b was determined.     

An investigation of the voltammetric characteristics of the osazone of dihydroxytartaric acid

Differential pulse polarography (d.p.p.), supplemented by other voltammetric techniques, is used to elucidate the tautomeric structures associated with buffered aqueous solutions of the osazone of dihydroxytartaric acid. In particular, d.p.p. is used to evaluate the number of electrons and protons associated with each of seven reduction processes, at pH values ranging from 2.5–11.5. The reversibility of the electrode processes is demonstrated by cyclic voltammetry and d.p.p. All the reduction processes studied are diffusion-controlled. Mechanisms for these reductions are proposed on the basis of the tautomeric equilibrium associated with the osazone in solution.