Ethylene glycol‐based ionic liquids via azide/alkyne click chemistry

A facile synthetic route for the preparation of dicationic ethylene glycol based‐ionic liquids (ILs) via the azide/alkyne “click” reaction is presented. The copper(I) catalyzed, microwave‐assisted azide/alkyne “click” reaction between diazido‐ethylene glycols and the corresponding alkyne containing IL‐head group enables a simple preparation of different sets of poly(ethylene glycol)‐based ILs. Beside tetra‐ and hexa(ethylene glycol)‐based ILs, also oligomeric (M_n = 400 g/mol) and polymeric ILs (M_n up to 1550 g/mol) could be prepared in good yield and with full conversion of the ionic head group. The prepared ILs were extensively characterized via NMR spectroscopy and ESI‐time‐of‐flight (TOF) mass spectroscopy, revealing the formation of multiply charged ions in the negative mode. Thermal stability proved to be exceptionally high (up to 300 °C) together with low glass‐transition temperatures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Dependence properties and comparison results for Lévy processes

In this paper we investigate dependence properties and comparison results for multidimensional Lévy processes. In particular we address the questions, whether or not dependence properties and orderings of the copulas of the distributions of a Lévy process can be characterized by corresponding properties of the Lévy copula, a concept which has been introduced recently in Cont and Tankov (Financial modelling with jump processes. Chapman & Hall/CRC, Boca Raton, 2004) and Kallsen and Tankov (J Multivariate Anal 97:1551–1572, 2006). It turns out that association, positive orthant dependence and positive supermodular dependence of Lévy processes can be characterized in terms of the Lévy measure as well as in terms of the Lévy copula. As far as comparisons of Lévy processes are concerned we consider the supermodular and the concordance order and characterize them by orders of the Lévy measures and by orders of the Lévy copulas, respectively. An example is given that the Lévy copula does not determine dependence concepts like multivariate total positivity of order 2 or conditionally increasing in sequence. Besides these general results we specialize our findings for subfamilies of Lévy processes. The last section contains some applications in finance and insurance like comparison statements for ruin times, ruin probabilities and option prices which extends the current literature. Anja Blatter was supported by the Deutsche Forschungsgemeinschaft (DFG).     

In vitro anticancer activity of binuclear Ru(II) complexes with Schiff bases derived from 5-substituted salicylaldehyde and 2-aminopyridine with notably low IC50 values

The binuclear Ru(II) complexes with Schiff bases derived from 5-chlorosalicyladehyde and 2-aminopyridine and its 5-substituted salicylideneimine homologues were tested in vitro against cervical carcinoma (HeLa), metastatic colorectal adenocarcinoma (SW620), lung adenocarcinoma (A549), breast adenocarcinoma (MCF-7), and human lung fibroblast (WI-38) cell lines. All compounds showed strong antiproliferative activity with extremely low IC₅₀ values. The compounds expressed strong activity against gram-positive bacteria, Staphylococcus aureus and Enterococcus faecalis.     

Heteroleptic ruthenium bioflavonoid complexes: from synthesis to in vitro biological activity

Heteroleptic ruthenium(II) bioflavonoid complexes of quercetin, morin, chrysin, and 3-hydroxyflavone were prepared and their interaction with CT DNA and BSA along with antioxidant and in vitro anticancer and antimicrobial activities was investigated. The formulation and characterization of complexes were achieved through elemental and thermal analysis, mass spectrometry, ¹H NMR spectroscopy along with infrared, electronic absorption, and emission spectroscopy as well as square-wave voltammetry, and magnetic and conductivity measurements. Ruthenium(II) is octahedrally coordinated in cationic complex species to two bidentate diimine ligands (2,2′-bipyridine or 1,10-phenanthroline) and one bidentate monobasic flavonoid ligand through 3,4-site of quercetin, morin, and 3-hydroxyflavone or 4,5-site of chrysin. Complexes bind CT DNA by intercalation and binding constants comparable to ethidium bromide or 10 times higher. Binding constants of complexes to BSA were several times higher compared to ibuprofen and diazepam, and suggest that the complexes have a strong affinity to BSA. Antioxidant activity tests showed that the complexes are more potent in terms of radical inhibition compared to the parent flavonoids. Cytotoxic testing revealed that the Ru(II) complex of quercetin with 2,2′-bipyridine co-ligand has good selectivity to breast adenocarcinoma, while the complex of 3-hydroxyflavone with 2,2′-bipyridine co-ligand showed strong cytotoxicity toward all tested cell lines with IC₅₀ ～ 1 μM. All complexes showed moderate activity toward Acinetobacter baumannii, while the Ru(II) complex of 3-hydroxyflavone with 2,2′-bipyridine showed excellent activity toward MRSA and Candida albicans.     

Synthesis and Molecular Structures of Tetrasilyl Ethers of Calix[4]arenes

The tetrasilyl ethers calix[4]areneOSiMe₂R (R = Me, H, vinyl, allyl) were prepared by salt elimination; the calix[4]arene was deprotonated with sodium hydride and subsequently reacted with chlorosilanes ClSiMe₂R. In general, DMF was chosen as solvent in order to steer the reactions in terms of a preference for the cone‐conformation of the products. In the case of calix[4]areneOSiMe₃ both, partial‐cone‐ and cone‐conformers, were synthesised. All products were characterised by NMR (¹H, ¹³C, ²⁹Si) spectroscopy, mass spectrometry and single‐crystal X‐ray diffraction.     

Magnetic nanostructures by adaptive twinning in strained epitaxial films

We exploit the intrinsic structural instability of the Fe(70)Pd(30) magnetic shape memory alloy to obtain functional epitaxial films exhibiting a self-organized nanostructure. We demonstrate that coherent epitaxial straining by 54% is possible. The combination of thin film experiments and large-scale first-principles calculations enables us to establish a lattice relaxation mechanism, which is not expected for stable materials. We identify a low twin boundary energy compared to a high elastic energy as key prerequisite for the adaptive nanotwinning. Our approach is versatile as it allows to control both, nanostructure and intrinsic properties for ferromagnetic, ferroelastic, and ferroelectric materials.