Mannich products of kojic acid and N-heterocycles and their Ru(II)-arene complexes: Synthesis, characterization and stability

Ru(II)-η⁶-p-cymene compounds bearing pyrone-derived ligands, which were obtained by Mannich reaction with piperidine and related analogues, have been synthesized. The compounds were characterized by NMR spectroscopy, mass spectrometry, thermogravimetric analysis and in the case of 2-(2,6-dimethyl-morpholin-4-ylmethyl)-3-hydroxy-6-hydroxymethyl-pyran-4-one by X-ray diffraction analysis. The chlorido complexes are prone to aquation in aqueous solution which results in the formation of dimers. Dimer formation can be inhibited by in situ replacement of the chlorido ligand by imidazole yielding compounds which are significantly more stable in water, as demonstrated by ¹H NMR spectroscopy.     

Recent developments in chromatographic fingerprints from herbal products: set-up and data analysis

The use of chromatographic fingerprints from herbal products where the whole chromatographic profile is applied to evaluate the quality of the investigated product. In this paper, recent developments in the set-up and data analysis of chromatographic fingerprints for herbal products are discussed. First different set-ups for fingerprint development are reviewed. Prior to fingerprint development, a suitable sample preparation, e.g. extraction, should be considered. In a second instance, this review focuses on the data analysis with regards to the different applications of fingerprints. Usually, chemometric data pretreatment is necessary. This is discussed first, followed by a short overview of the data handling techniques used in the two main application areas of herbal fingerprints, i.e. quality assurance and classification or calibration. The quality assurance, which involves the identification and quality control of the herbal products, is reviewed, followed by the use of fingerprints in classification or modelling. The different application areas are illustrated and discussed with several case studies.     

AT‐Specific DNA Binding of Binuclear Ruthenium Complexes at the Border of Threading Intercalation

The binuclear ruthenium complex [μ‐bidppz(phen)₄Ru₂]⁴⁺ has been extensively studied since the discovery of its unusual threading intercalation interaction with DNA, a binding mode with extremely slow binding and dissociation kinetics. The complex has been shown to be selective towards long stretches of alternating AT base pairs, which makes it interesting, for example, as a model compound for anti‐malaria drugs due to the high AT content of the genome of the malaria parasite P. falciparum. We have investigated the effect of bridging ligand structure on threading intercalation ability and found that length and rigidity as well as the size of the intercalated ring system are all factors that affect the rate and selectivity of the threading intercalation. In particular, we discovered a new DNA‐threading compound, [μ‐dppzip(phen)₄Ru₂]⁴⁺, which appears to be just at the border of being capable of threading intercalation and displays even greater selectivity for AT‐DNA than the parent compound, [μ‐bidppz(phen)₄Ru₂]⁴⁺.     

Non-universal shear viscosity from Einstein gravity

A very famous result of gauge/gravity duality is the universality of the ratio of shear viscosity to entropy density in every field theory holographically dual to classical, two-derivative (Einstein) gravity. We present a way to obtain deviation from this universality by breaking the rotational symmetry spontaneously. In anisotropic fluids additional shear modes exist and their corresponding shear viscosities may be non-universal. We confirm this by explicitly calculating the shear viscosities in a transversely isotropic background, a p-wave superfluid, and study its critical behavior. This is a first decisive step towards further applications of gauge/gravity duality to physical systems.     

On the Number of Distinct Values of a Class of Functions with Finite Domain

By relating the number of images of a function with finite domain to a certain parameter, we obtain both an upper and lower bound for the image set. Even though the arguments are elementary, the bounds are, in some sense, best possible. These bounds are then applied in several contexts. In particular, we obtain the first non-trivial upper bound for the image set of a planar function over a finite field.     

Adaptive nonparametric estimation for Lévy processes observed at low frequency

This article deals with adaptive nonparametric estimation for Lévy processes observed at low frequency. For general linear functionals of the Lévy measure, we construct kernel estimators, provide upper risk bounds and derive rates of convergence under regularity assumptions.     

Model reduction and dynamic iteration for coupled nonlinear systems

The dynamical behavior of coupled systems is determined by different interconnected subsystems that are usually governed by entirely different physical laws and often act in different time and space scales. We discuss the simulation of coupled nonlinear systems using dynamic iteration combined with model order reduction. We also study the convergence of this approach and derive error estimates for approximate solutions. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Organocatalytic asymmetric fulvene formation

The first catalytic asymmetric formation of a fulvene from a racemic α,α-disubstituted aldehyde has been developed. Dynamic kinetic resolution of rac-2-phenylpropanal by a simple, modularly designed supramolecular organocatalyst consisting of inexpensive components has been established, producing the desired fulvene in good yields and moderate enantioselectivities. Herein we propose a mechanistic interpretation of the observed solvent- and additive-induced stereoselectivity reversal.