Approaches to Model Nanotube-Reinforced Polymers using Micromechanics and Finite Elements

In this work, the applicability of new analytical methods for modeling polymer nanocomposites is examined. The influence of an interphase between nanotube and matrix could be captured by this modeling strategy. However, it is shown that there are some difficulties in calculation of composites including extremely weak fibers with stiff coatings. Furthermore, finite element calculations are shown for comparison. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

l‐Seryl‐l‐phenyl­alanine

The peptide bond in the crystal structure of the title compound, C₈H₁₆N₂O₄, deviates substantially from planarity in the same manner as in other l ‐Ser‐l ‐Xaa dipeptides, where Xaa is a hydro­phobic residue.     

Palladium‐Catalyzed Decarboxylative γ‐Arylation for the Synthesis of Tetrasubstituted Chiral Allenes

An enantiospecific palladium‐catalyzed decarboxylative coupling of acyclic β,γ‐alkynoic acids with various aryl iodides to chiral tetrasubstituted allenes is described. The coupling reaction comprises a decarboxylative γ‐palladation of α,α‐disubstituted carboxylic acids to provide the tetrasubstituted allenes with complete point‐to‐axial chirality transfer in excellent yields.     

Comparison of analytical and numerical methods for homogenization of nanotube-reinforced polymers

Carbon nanotubes are increasingly getting impact as reinforcing material for polymer based nanocomposites. Hence, new modeling strategies are necessary to calculate the behavior of these materials. In the last years some attempts have been made using and developing classical micromechanical models. On the other hand numerical homogenization methods are available to tackle this problem. Examples for both types of modeling strategies are presented with focus on the nanotube geometry. The nanotubes are modeled as hollow tubes as well as as isotropic and transversely isotropic cylinders. As expected the results of numerical and analytical methods are identical for isotropic cylinder inclusions. Small deviations occur for transversely isotropic cylinders in transverse direction. In the case of hollow tube inclusions, the analytical models lead to lower stiffness values in transverse direction and for shear. The largest deviations occur for longitudinal shear with magnitudes smaller than 10%. In contrast the effort to get numerical results is enormous, so that the analytical models are still useful. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fully Bridged Triphenylamines Comprising Five- and Seven-Membered Rings

A family of fully bridged triphenylamines with embedded 5- and 7-membered rings is presented. The compounds are potent electron donors capable to undergo donor/acceptor interactions with strong cyano-based acceptors both in the solid state and solution. These interactions were evaluated by IR and UV/vis spectroscopy as well as X-ray crystallography. The vinylene-bridged compound was oxidized to the corresponding 1,2-diketone which readily underwent acid-catalyzed condensation with selected 1,2-phenylenediamines. The resulting π-extended quinoxaline derivatives represent valuable building blocks for the development of functional chromophores upon appropriate functionalization.     

Stress-induced transformation behavior of a polycrystalline NiTi shape memory alloy: micro and macromechanical investigations via in situ optical microscopy

An experimental investigation of the micro and macromechanical transformation behavior of polycrystalline NiTi shape memory alloys was undertaken. Special attention was paid to macroscopic banding, variant microstructure, effects of cyclic loading, strain rate and temperature effects. Use of an interference filter on the microscope enabled observation of grain boundaries and martensitic plate formation and growth without recourse to etching or other chemical surface preparation. Key results of the experiments on the NiTi include observation of localized plastic deformation after only a few cycles, excellent temperature and stress relaxation correlation, a refined definition of “full transformation” for polycrystalline materials, and strain rate dependent effects. Several of these findings have critical implications for understanding and modeling of shape memory alloy behavior.     

1,x-elimination reactions: extending the limits of a classical organic reaction

Alpha,omega-dibromo derivatives in which the two terminal carbon atom are separated by an unsaturated spacer unit ("pi spacer") undergo 1,x-elimination reactions (with x=6, 8, 10, and 14), using Mori's reagent (nBu3SnSiMe3/CsF). The resulting cumulenic intermediates cyclodimerize in a subsequent step yielding novel macrocyclic acetylenic and bridged aromatic compounds (cyclophanes). Thus 1,6-eliminations were carried out with dibromide 17 to yield 1,3,7,9-cyclododecatetrayne (20) and with benzylbromide 24 to provide cyclophanes 26 and 27. By 1,8-eliminations the 16-membered macrocycle 33 could be prepared from enediyne 31, the benzannelated 1,5-cyclooctadiyne 41 from dibromide 38, and a mixture of cyclophanes 45 and 46 from the precursor 43. 1,10-Eliminations were carried out successfully with dibromides 47, 50, and 53 yielding the corresponding unsaturated cyclophanes ("cyclophynes") 49, 52, and 55. The influence of the solvent on the cyclodimerization 47-->49 was investigated, with acetonitrile providing the highest yields. The heterophanes 59 a and b were obtained by 1,10-elimination of the precursor dibromides 57 a and b, and in an elimination experiment involving a 1:1 mixture of the dibromides 50 and 57 b the "mixed dimer" 60 was isolated, besides the homodimers 52 and 59 b. The method reached its limits with the 1,14-elimination of 68, 70, and 74 providing the cyclophanes 69, 71, and 75 in varying amounts. Two final debrominations with 76 and 77, which in principle could undergo 1,16- and 1,20-eliminations reactions, respectively, failed. The structures of the new cyclophanes 49, 50, 59 a, and 59 b were established by X-ray structural analysis; all other structure assignments rest on the usual spectroscopic and analytical data.     

(Metallo)porphyrins as Potent Phototoxic Anti‐Cancer Agents after Irradiation with Red Light

Novel photoactive (metallo)porphyrins were synthesised and characterised. When irradiated with light at a wavelength greater than 600 nm, these porphyrins act as photosensitisers and show high cytotoxicity towards two different human cancer cell lines with IC₅₀ values down to 0.4 μM . A paramagnetic copper(II) porphyrin is the first photosensitiser to display excellent phototoxicity, explained by the electron paramagnetic resonance (EPR) spin trapping of hydroxy radicals and experimentally confirmed by the discovery of elevated levels of reactive oxygen species (ROS) inside A2780 cells after irradiation with red light. This finding indicates that paramagnetic compounds should be considered for photodynamic therapy (PDT). Furthermore, an additive effect of cisplatin and a zinc porphyrin, both at subtherapeutic concentrations of 0.22 μm, was observed.