Synthesis of selenium- and tellurium-containing nucleosides derived from uridine

The synthesis of selenium- and tellurium-containing nucleosides, derived from uridine is described herein. These compounds were prepared in a concise and short synthetic route in good yields, by nucleophilic substitution of a tosylate group by organoselenium nucleophiles.     

Raman scattering from CuBr and CuI

Detailed temperature-dependent Raman spectra of CuI and CuBr are reported for the first time. Spectra have been recorded between room temperature and 6K. Peaks arising from scattering by the zone-center optic phonon modes have been identified and their frequencies compared with those determined by neutron scattering and infrared measurements. The LO phonon energy in CuBr is found to reflect the negative thermal expansion at low temperatures while the TO phonon frequency does not follow this behavior. Second-order features of the CuI spectrum are identified using available phonon dispersion curves.     

Electrodeposition of nanocrystalline aluminium from a chloroaluminate ionic liquid

In this letter we show that nanocrystalline aluminium can be electrodeposited in the Lewis acidic ionic liquid based on AlCl₃ (60 mol%) and 1-(2-methoxyethyl)-3-methylimidazolium chloride ([MoeMIm]Cl) (40 mol%). The study comprised cyclic voltammetry, potentiostatic polarization, and SEM and XRD measurements. The methoxy group in the side chain of the imidazolium cation significantly influences the electrodeposition pathway of Al in comparison to [EMIm]Cl/AlCl₃. Cyclic voltammetry shows a significant current loop attributed to nucleation. Shiny Al layers are obtained with an average crystallite size of about 40 nm.     

On the electronic structure of the hydrogenase H-cluster

X-ray absorption spectroscopic measurements and density functional calculations suggest that the hydrogenase H-cluster is best described as an electronically inseparable 6Fe-cluster due to extensive delocalization of frontier molecular orbitals of the iron centres, sulfide and the non-innocent dithiolate ligands.     

New aspects of B → ππ, πK and their implications for rare decays

We analyze the B → ππ, πK modes in the light of the most recent B-factory data, and obtain the following new results: (i) the modes prefer γ = (74±6)°, which - together with |V_ub/V_cb| - allows us to determine the "true" unitarity triangle and to search for CP-violating new-physics contributions to B⁰_d- mixing; (ii) the B → πK puzzle reflected in particular by the low experimental value of the ratio R_n of the neutral B → πK rates persists and still favors new physics in the electroweak penguin sector with a new CP-violating phase ϕ ~ –90°, although now also ϕ ~ +90° can bring us rather close to the data; (iii) the mixing-induced CP asymmetry is a sensitive probe of the sign of this phase, and would currently favor ϕ ~ +90°, as well as the direct CP asymmetry of , which suffers, however, from large hadronic uncertainties; (iv) we investigate the sensitivity of our B → πK analysis to large non-factorizable SU(3)-breaking effects and find that their impact is surprisingly small so that it is indeed exciting to speculate on new physics; (v) assuming that new physics enters through Z⁰ penguins, we study the interplay between B → πK and rare B, K decays and point out that the most recent B-factory constraints for the latter have interesting implications, bringing us to a few scenarios for the future evolution of the data, where also the mixing-induced CP violation in plays a prominent r?le.     

Triplet Emitting C^N^C Cyclometalated Dibenzo[c,h]Acridine Pt(II) Complexes

In a series of Pt(II) complexes [Pt(dba)(L)] containing the very rigid, dianionic, bis-cyclometalating, tridentate C^N^C²⁻ heterocyclic ligand dba^2– (H₂dba = dibenzo[c,h]acridine), the coligand (ancillary ligand) L = dmso, PPh₃, CNtBu and Me₂Imd (N,N’-dimethylimidazolydene) was varied in order to improve its luminescence properties. Beginning with the previously reported dmso complex, we synthesized the PPh₃, CNtBu and Me₂Imd derivatives and characterized them by elemental analysis, ¹H (and ³¹P) NMR spectroscopy and MS. Cyclic voltammetry showed partially reversible reduction waves ranging between −1.89 and −2.10 V and increasing along the series Me₂Imd < dmso ≈ PPh₃ < CNtBu. With irreversible oxidation waves ranging between 0.55 (L = Me₂Imd) and 1.00 V (dmso), the electrochemical gaps range between 2.65 and 2.91 eV while increasing along the series Me₂Imd < CNtBu < PPh₃ < dmso. All four complexes show in part vibrationally structured long-wavelength absorption bands peaking at around 530 nm. TD-DFT calculated spectra agree quite well with the experimental spectra, with only a slight redshift. The photoluminescence spectra of all four compounds are very similar. In fluid solution at 298 K, they show broad, only partially structured bands, with maxima at around 590 nm, while in frozen glassy matrices at 77 K, slightly blue-shifted (~580 nm) bands with clear vibronic progressions were found. The photoluminescence quantum yields Φ_L ranged between 0.04 and 0.24, at 298 K, and between 0.80 and 0.90 at 77 K. The lifetimes τ at 298 K ranged between 60 and 14040 ns in Ar-purged solutions and increased from 17 to 43 µs at 77 K. The TD-DFT calculated emission spectra are in excellent agreement with the experimental findings. In terms of high Φ_L and long τ, the dmso and PPh₃ complexes outperform the CNtBu and Me₂Imd derivatives. This is remarkable in view of the higher ligand strength of Me₂Imd, compared with all other coligands, as concluded from the electrochemical data.     

Approximation on Simplices with Respect to Weighted Sobolev Norms

Inequalities of Jackson and Bernstein type are derived for polynomial approximation on simplices with respect to Sobolev norms. Although we cannot use orthogonal polynomials, sharp estimates are obtained from a decomposition into orthogonal subspaces. The formulas reflect the symmetries of simplices, but analogous estimates on rectangles show that we cannot expect rotational invariance of the terms with derivatives.     

Wavelet approximations for first kind boundary integral equations on polygons

Summary. An elliptic boundary value problem in the interior or exterior of a polygon is transformed into an equivalent first kind boundary integral equation. Its Galerkin discretization with degrees of freedom on the boundary with spline wavelets as basis functions is analyzed. A truncation strategy is presented which allows to reduce the number of nonzero elements in the stiffness matrix from to entries. The condition numbers are bounded independently of the meshwidth. It is proved that the compressed scheme thus obtained yields in operations approximate solutions with the same asymptotic convergence rates as the full Galerkin scheme in the boundary energy norm as well as in interior points. Numerical examples show the asymptotic error analysis to be valid already for moderate values of . Received March 12, 1994 / Revised version received January 9, 1995