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.     

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.     

Biradical character of linear π-conjugated oligomer dications composed of thiophene, pyrrole, and methylthio end-capping units

Combined DFT calculations and UV-vis-NIR, ESR, and SQUID measurements revealed that the ground-state electronic structure of a linear π-conjugated oligomer dication composed of two pyrrole and six or seven thiophene rings and methylthio end-capping units is dominated by a singlet biradical character.     

Test compounds for detecting the silanol effect on the elution of ionized amines in reversed‐phase LC

The effectiveness of several basic compounds for testing silica‐based stationary phases was reviewed by applying them to recent columns for reversed‐phase HPLC. Most octadecylsilylated (C18) stationary phases, prepared as a base‐deactivated material from high‐purity silica gel with endcapping, provided excellent peak shape and column efficiency for the bases including benzylamine and amitriptyline that once caused problems and were subsequently employed for testing silanol activities. However, a cyclic tertiary amine, dextrometorphan, was eluted as an acceptable peak from only a few columns at neutral pH. Such a more sensitive probe is expected to contribute to further improvement of the stationary phase for reversed‐phase HPLC.     

Impact of valley polarization on the resistivity in two dimensions

We examine the temperature dependence of resistivity in a two-dimensional electron system formed in a silicon-on-insulator quantum well. The device allows us to tune the valley splitting continuously in addition to the electron density. Our data provide a global picture of how the resistivity and its temperature dependence change with valley polarization. At the boundary between valley-polarized and partially polarized regions, we demonstrate that there is an insulating contribution from spin-degenerate electrons occupying the upper valley-subband edge.