Persistent pi radical cations: self-association and its steric control in the condensed phase

Pi Radical cations, which are highly reactive in general, can be made persistently stable by appropriate structural modification with heteroatoms, pi-conjugated systems, and alkyl substituents. Many of these pi radical cations undergo self-association in the condensed phase. The steric control of such self-association of stabilized pi radical cations is the subject of the present article. Such an association can result in the formation of pi- and/or sigma-dimers. The pi-dimerization in particular is now considered as an important intermolecular interaction for model studies of a charge-transport phenomenon in positively doped conducting polymers. On the other hand, the intermolecular interactions can be suppressed when the pi-system is modified with sterically demanding structural units, for example, by annelation with bicycloalkene frameworks. This structural modification not only brings about unusual stabilization of the radical cations but provides valuable information on the electronic structure/properties of the positively charged pi-systems in a segregated state.     

The first samarium(II)-mediated aryl radical cyclisation onto an aromatic ring

Intramolecular arylation of aryl radicals was mediated by SmI(2)/HMPA in the presence of i-PrOH to give spirocycles and/or reduced cine-cyclised products, while the reaction in the absence of i-PrOH gave the rearomatised fused rings.     

First results from KamLAND: evidence for reactor antineutrino disappearance

KamLAND has measured the flux of nu;(e)'s from distant nuclear reactors. We find fewer nu;(e) events than expected from standard assumptions about nu;(e) propagation at the 99.95% C.L. In a 162 ton.yr exposure the ratio of the observed inverse beta-decay events to the expected number without nu;(e) disappearance is 0.611+/-0.085(stat)+/-0.041(syst) for nu;(e) energies >3.4 MeV. In the context of two-flavor neutrino oscillations with CPT invariance, all solutions to the solar neutrino problem except for the "large mixing angle" region are excluded.     

Total synthesis of leustroducsin B

A convergent total synthesis of leustroducsin B (1), which is known to exhibit a variety of biological activities, was successfully carried out. Notable features of our synthesis include construction of the C8 stereocenter by lipase-mediated desymmetrization of meso-diol 4 (90.2% ee) and preparation of the C9-C11 anti-diol moiety by the addition of alkynylzinc reagent 20 to the aldehyde 19. Furthermore, a new diol protecting group, p-silyloxybenzylidene, was developed for the deprotection from densely functionalized substrates under weakly acidic conditions. The protecting group was easily removed in a two-step procedure ((HF)3.Et3N; AcOH-THF-H2O).     

Structural Analysis of Electroplated Amorphous-Nanocrystalline Ni-W

 Ductile nickel-tungsten (Ni-W) alloys containing about 20–21 at.%W were electroplated onto copper substrates. The development of the amorphous/nanocrystalline microstructure towards a complete crystallization by isochronal heat treatments in vacuum was monitored by different methods. For medium annealing temperatures a solid-solution of W in the fcc-Ni lattice was achieved resulting in an increased hardness. For temperatures of 600 °C and upward recrystallization started and thermodynamically stable intermetallic compounds like Ni₄W and NiW were formed. A third phase, containing more than 80 at.%W was also detected but could not be identified so far. Only by combination of different methods and especially by use of analytical TEM structural analysis and phase identification in these amorphous-nanocrystalline Ni-W alloys were successful.     

On the analysis of intermediate–energy Coulomb excitation experiments

In a recent publication [C.A. Bertulani, G. Cardella, M. De Napoli, G. Raciti, E. Rapisarda, Phys. Lett. B 650 (2007) 233] the validity of analysis methods used for intermediate-energy Coulomb excitation experiments was called into question. Applying a refined theory large corrections of results in the literature seemed needed. We show that this is not the case and that the large deviations observed in above mentioned reference are due to the use of the wrong experimental parameters in that publication. We furthermore show that an approximate expression derived in above mentioned reference is in fact equivalent to the theory of Winther and Alder, an analysis method often used in the literature.