Synthese, 13C-NMR-Spektren und räumliche Struktur von ‘Push-Pull’-Diacetylenen

Synthesis, ¹³C-NMR Spectra, and X-Ray Investigation of ‘Push-Pull’ Diacetylenes Phenyl-substituted ‘push-pull’ diacetylenes 1f and 1g have been prepared by acetylation and benzoylation of the appropriate lithiodiynylamines 4 (Scheme 2). ¹³C-NMR spectra of diacetylenes 1a–g (Table 1) are discussed with respect to the expected polarisation of the diacetylene unit by ‘push’ and ‘pull’ substituents. X-Ray investigations of 1c , 1e , and 1f have been performed in view of the planned solid-state polymerisation of ‘push-pull’ diacetylenes. In the crystalline state, diacetylenes 1c and 1f are stacked, however, the stacking parameters do not allow a solid-state polymerisation.     

Polygonal finite element formulations for 2d linear-elastic FE problems

Polygonal finite elements provide great flexibility meshing complex structures and for the refinement of meshes. The actual task in the development of these elements is to offer adequate and secure numerical results compared with regular finite elements at low computational costs. Particulary, finding an efficient and appropriate interpolation of the arbitrary element domain exhibits strong difficulties. Based on the general interpolant equation three element formulations are shown that use different interpolation strategies. The elements' performances are shown with a numerical example considering 2d linear elasticity. The results of the different element formulations are compared among each other, with analytical as well as with regular elements' results. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Efficient Synthesis of Cryptophycin‐52 and Novel para‐Alkoxymethyl Unit A Analogues

Cryptophycins are a family of highly cytotoxic, cyclic depsipeptides. They display antitumour activity that is largely maintained for multi‐drug‐resistant tumour cells. Cryptophycins are composed of four building blocks (units A–D) that correspond to the respective amino and hydroxy acids. A new synthetic route to unit A allows the selective generation of all four stereogenic centres in a short, efficient and reliable synthesis and contributes to an easier and faster synthesis of cryptophycins. The first two stereogenic centres are introduced by a catalytic asymmetric dihydroxylation, whereas the remaining two stereogenic centres are introduced with substrate control of diastereoselectivity. The stereogenic diol function also serves as the epoxide precursor. The approach was used to synthesise the native unit A building block as well as three para‐alkoxymethyl analogues from which cryptophycin‐52 and three analogous cryptophycins were prepared. Macrocyclisation of the seco‐depsipeptides was based on ring‐closing metathesis.     

The Thermodynamic Influence of Trapped Water Molecules on a Protein–Ligand Interaction

Water molecules doing time : Atomic‐resolution crystal structures of the PPIase domain of cyclophilin G, alone and in complex with cyclosporin A, and together with MD simulations and calorimetry, reveal how trapped water molecules influence the thermodynamic profile of a protein–ligand interaction.

     

Improved approximation algorithms for metric maximum ATSP and maximum 3-cycle cover problems

We consider an -hard variant (Δ-Max-ATSP) and an -hard relaxation (Max-3-DCC) of the classical traveling salesman problem. We present a -approximation algorithm for Δ-Max-ATSP and a -approximation algorithm for Max-3-DCC with polynomial running time. The results are obtained via a new way of applying techniques for computing undirected cycle covers to directed problems.