Podophyllotoxin aza-analogue, a novel DNA topoisomerase II inhibitor

The pendant E-ring moiety of the podophyllotoxin aza-analogue 1 that is a potent inhibitor of microtubule assembly was modified in order to acquire inhibitory activity of DNA topoisomerase II. The monophenolic analogue 2 did not exhibit human topoisomerase II inhibition, while the ortho-quinone 3 that was obtained by oxidation of 2 inhibited its catalytic activity (decatenation) in a dose-dependent manner and stimulated double strand DNA breaks in supercoiled circular plasmid DNA, resulting in the production of linear DNA. These results showed that the topoisomerase II inhibition of the ortho-quinone 3 is due to stabilization of the topoisomerase II-DNA covalent binary complex. On the other hand, the ortho-quinone 3 did not inhibit the relaxation process of supercoiled DNA by topoisomerase I at concentrations up to 400 microM, nor was intercalation observed in unwinding measurements of 3. Therefore, the ortho-quinone 3 was shown to be a novel nonintercalative topoisomerase II specific inhibitor that stabilizes the cleavable complex. The present results suggest that the 4'-free hydroxyl group on the E-ring and the sugar moiety on the C-ring are not a prerequisite for topoisomerase II inhibition by podophyllotoxin derivatives.     

An efficient chiral synthesis of (+)-sesbanine

(+)-Sesbanine was effectively synthesized from 4-methylnicotinonitrile and 1-malic acid.     

An asymmetric synthesis of cis,anti, cis-tricyclo[5,3,0,02,6]decanes applying γ-hydroxymethyl-γ-butyrolactone as a chiral synthon. First asymmetric total synthesis of (−)-β-bourbonene

The asymmetric total synthesis of cis, anti, cis-tricyclo[5,3,0,0^2,6]decane sesquiterpene β-bourbonene is described. The key (2+2) photocycloaddition was carried out applying the optically pure butenolide derivative $\text{6b}$ as a chiral synthon.     

Preparation of sterically congested di(4-pyridyl)diazomethanes and characterization of triplet carbenes from them

Di(4-pyridyl)diazomethanes having two and four ortho chlorine groups were prepared, and the triplet carbenes generated from them were characterized by ESR and UV/vis at low temperature and time-resolved UV/vis at room temperature. An appreciable increase in the stability of triplet carbenes is achieved by introducing ortho chlorine groups. [structure: see text]     

d-d excitations in manganites probed by resonant inelastic x-ray scattering

We report a study of electronic excitations in manganites exhibiting a range of ground states, using resonant inelastic x-ray scattering (RIXS) at the Mn K edge. Excitations with temperature dependent changes correlated with the magnetism were observed as high as 10 eV. By calculating Wannier functions, and finite-q response functions, we associate this dependence with intersite d-d excitations. The calculated dynamical structure factor is found to be similar to the RIXS spectra.     

Orbital nature of ferromagnetic magnons in manganites

Magnon excitation in a ferromagnetic state of Sm(0.55)Sr(0.45)MnO(3) located on the verge of the metal-insulator transition has been studied in terms of the neutron scattering experiment. The anomalous magnon dispersion with the zone-boundary softening is well described by the Heisenberg model with extended exchange coupling constants J(s). In particular the fourth neighbor coupling J(4) is as large as 0.6 times the nearest neighbor one J(1). Theoretical analysis based on the local density approximation + Hubbard U band calculation reveals that this one-dimensional exchange path is due to the (3z(2)-r(2))-type orbital correlation, in sharp contrast to previous proposals.     

Soft x-ray resonant diffraction study of magnetic and orbital correlations in a manganite near half doping

We have utilized resonant x-ray diffraction at the Mn L(II,III) edges in order to directly compare magnetic and orbital correlations in Pr0.6Ca0.4MnO3. Comparing the widths of the magnetic and orbital diffraction peaks, we find that the magnetic correlation length exceeds that of the orbital order by nearly a factor of 2. Furthermore, we observe a large (approximately 3 eV) spectral weight shift between the magnetic and orbital resonant line shapes, which cannot be explained within the classic Goodenough picture of a charge-ordered ground state. To explain the shift, we calculate the orbital and magnetic resonant diffraction line shapes based on a relaxed charge-ordered model.