A Surprising Adduct of a closo Cluster

The geometry of the Si ₂ B ₁₀ framework remains nearly unchanged when the Si–Si edge is bridged by an electron-donating amido group. This finding is clearly evident from the single-crystal X-ray structure analysis and ab initio calculations of the uprecedented adduct that is formed by the addition of Et₂N⁻ to o-silaborane (structure depicted bottom right).     

(2′‐O‐Methyl‐RNA)‐3′‐PNA Chimeras: A New Class of Mixed Backbone Oligonucleotide Analogues with High Binding Affinity to RNA

The automated on‐line synthesis of DNA‐3′‐PNA chimeras 1 – 4 and (2′‐O‐methyl‐RNA)‐3′‐PNA chimeras 5 – 8 is described, in which the 3′‐terminal part of the oligonucleotide is linked to the N‐terminal part of the PNA via N‐(ω‐hydroxyalkyl)‐N‐[(thymin‐1‐yl)acetyl]glycine units (alkyl=Et, Ph, Bu, and pentyl). By means of UV thermal denaturation, the binding affinities of all chimeras were directly compared by determining their T_m values in the duplex with complementary DNA and RNA. All investigated DNA‐3′‐PNA chimeras and (2′‐O‐methyl‐RNA)‐3′‐PNA chimeras form more‐stable duplexes with complementary DNA and RNA than the corresponding unmodified DNA. Interestingly, a N‐(3‐hydroxypropyl)glycine linker resulted in the highest binding affinity for DNA‐3′‐PNA chimeras, whereas the (2′‐O‐methyl‐RNA)‐3′‐PNA chimeras showed optimal binding with the homologous N‐(4‐hydroxybutyl)glycine linker. The duplexes of (2′‐O‐methyl‐RNA)‐3′‐PNA chimeras and RNA were significantly more stable than those containing the corresponding DNA‐3′‐PNA chimeras. Surprisingly, we found that the charged (2′‐O‐methyl‐RNA)‐3′‐PNA chimera with a N‐(4‐hydroxybutyl)glycine‐based unit at the junction to the PNA part shows the same binding affinity to RNA as uncharged PNA. Potential applications of (2′‐O‐methyl‐RNA)‐3′‐PNA chimeras include their use as antisense agents acting by a RNase‐independent mechanism of action, a prerequisite for antisense‐oligonucleotide‐mediated correction of aberrant splicing of pre‐mRNA.     

Fourier–Finite-element Approximation of Elliptic Interface Problems in Axisymmetric Domains

The paper deals with the Fourier-finite-element method (FFEM), which combines the approximate Fourier method with the finite-element method, and its application to Poisson-like equations −p̂Δ₃û = f̂ in three-dimensional axisymmetric domains Ωˆ. Here, pˆ is a piecewise constant coefficient having a jump at some axisymmetric interface. Special emphasis is given to estimates of the Fourier-finite-element error in the Sobolev space H¹(Ωˆ), if the interface is smooth or if it meets the boundary of Ωˆ at some edge. In general, the solution û contains a singularity at the interface, which is described by a tensor product representation and treated numerically by appropriate mesh grading in the meridian plane of Ωˆ. The rate of convergence of the combined approximation in H¹(Ωˆ) is proved to be 𝒪(h+N⁻¹) (h, N: the parameters of the finite-element- and Fourier-approximation, with h→0, N→∞). The theoretical results are confirmed by numerical experiments.     

Smectic liquid single crystal elastomers

In the liquid crystalline (I.c.) state the backbone of l.c-polymers has to adapt an anisotropic conformation that is consistent with the I.c.-phase structure. For macroscopically uniformly aligned samples this anisotropic backbone conformation can be obtained by applying a suitable mechanical field on chemically crosslinked I.c-polymers. Introducing the network anisotropy a priori by synthesis, stable macroscopically aligned I.c.-networks can be realized. We have called these networks Liquid Single Crystal Elastomers (LSCE) because their physical properties resemble that of organic or inorganic single crystals.     

Bidentate Lewis Acids Derived from o‐Diethynylbenzene with Group 13 and 14 Functions

Starting from 1,2‐diethynylbenzene, a series of bidentate Lewis acids was prepared by means of hydrometalations, in particular hydrosilylation, hydroboration, hydroalumination and terminal metalation based on group 13 and 14 elements. In the case of terminal alkyne metalation, the Lewis‐acidic gallium function was introduced using triethylgallium under alkane elimination. A total of six different Lewis acids based on a semiflexible organic scaffold were prepared, bearing −SiClMe₂, −SiCl₂Me, −SiCl₃, −B(C₆F₅)₂, −AlBis₂ (Bis=bis(trimethylsilyl)methyl) and −GaEt₂ as the corresponding functional units. In all cases, the Lewis acid functionalisation was carried out twice and the products were obtained in good to excellent yields. In the case of the twofold gallium Lewis acid, a different structural motif in the form of a polymer‐like chain was observed in the solid state. All new bidentate Lewis acids were characterised by multinuclear NMR spectroscopy, CHN analysis and X‐ray diffraction experiments.     

Elongational Viscosity and Foaming Behavior of PP Modified by Electron Irradiation or Nanotube Addition

Summary : In this study, two different routes were chosen which are expected to influence the elongational viscosity and, thus, the foaming behavior of polypropylene (PP). Electron irradiation of a linear PP was performed at room temperature using different doses. Enhanced long-chain branching was observed with increased irradiation dose. In addition, a linear PP was filled with 5 wt% multiwalled carbon nanotubes (MWNT) by melt mixing at 200 °C. These modified PP materials were investigated with respect to their shear and elongational behavior. After foaming, irradiated PP led to an expansion factor which is about 60% higher than that of the non-irradiated product. In case of PP filled with 5 wt% MWNT the value of the expansion factor is about 70% higher than that of pure PP expanded under the same conditions. The cell structure is much finer in both cases as compared to unmodified PP.