Bent Phosphaallenes With “Hidden” Lone Pairs as Ligands

Phosphaheteroallenes R−P=C=L, with L = N-heterocyclic carbenes (NHCs), can be viewed to a certain extent as phosphaisonitriles stabilized with NHCs, R−P=C:←L. The suitability of these molecules as ligands for coinage-metal ions was investigated and coordination through the central carbon center was observed in most cases. A combination of experiments, spectroscopic methods, and DFT calculations indicates the presence of a hidden electron pair at the carbon center of R−P=C:←L. Remarkably, this lone pair also inserts intramolecularly in C−H bonds showing the carbene-type reactivity which is expected for phosphaisonitriles.     

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.     

Halbgruppen und semilineare Anfangs-Randwertprobleme

A semilinear parabolic initial-boundary-value problem of order 2m in a possibly unbounded domain Ωx(O,T), Ω?Rⁿ, is considered within the framework of the L_p-and C^α-theory. In the first case a proof is given of the existence of a “strict” solution of the corresponding evolution equation. In the second case one can guarantee a classical solution, provided the homogeneous linear parabolic equation has a unique classical solution. Only local solvability is considered. The nonlinearity is a Hölder-continuous function of the derivatives up to the order 2m-1 of the unknown solution. The principal tool is the semigroup-theory in L_p(Ω) as well as in C^α( \(\bar \Omega \) ). In the latter case the semigroup is not strongly continuous, but it has sufficiently good properties to use it for existence proofs of classical solutions.     

Dietary lipid content influences the activity of lipogenic enzymes in the liver and on whole body delta13C values of Nile tilapia, Oreochromis niloticus (L.)

The use of stable isotope techniques for the reconstruction of diets has increased over the last decade. However, isotopic ratios in an animal are not only affected by the composition of the feed, but also by the amount of feed consumed. An uncertainty of up to 1 per thousand for both delta13C and delta15N values has been observed when the feeding level is unknown. This may have substantial effects on the results of back-calculation. As the feeding level of animals is unknown in nature, an additional indicator for their nutritional status is needed. High feeding levels and a consequent surfeit of dietary energy lead to the synthesis of lipids. In order to test whether the level of lipogenesis could be used as an indicator, Nile tilapia (Oreochromis niloticus) were fed four isonitrogenous and isoenergetic wheat-based semi-synthetic diets with different lipid contents (2.0 %, 4.5 %, 9.5 % and 13.3 %) for eight weeks. Body composition, gross energy content and delta13C values in the lipids and the lipid-free material were determined in diets and fish bodies. The livers of three fish per feeding group were assayed for the activity of two lipogenic enzymes, ATP-citrate lyase and malic enzyme. There was a strong negative correlation between delta13C values in the lipids of the individual fish and the apparent lipid conversion. The activities of lipogenic enzymes decreased with rising lipid content in the diet. The delta13C values in the lipids decreased significantly with increasing specific activity for both enzymes. In this experiment where lipogenesis was influenced by the composition of the diet, it was possible to determine the exact value for the trophic shift in relation to the enzyme activities. Further experiments to investigate the use of enzyme activities in situations where the feeding level of an animal is unknown are recommended.     

Direct EPR detection of transient and continuous wave signals at 2.5 GHz

Direct detection of free induction decays and electron spin echoes, and the recording of echo-detected EPR spectra and electron spin echo envelope modulation patterns at a microwave frequency of 2.5 GHz is demonstrated. This corresponds to the measurement of the transverse magnetization in the laboratory frame, rather than in the rotating frame as usually done by down-converting the signal (homodyne detection). An oscilloscope with a 6-GHz analog bandwidth, a sampling rate of 20 GigaSamples per second, and a trigger frequency of 5 GHz for the edge trigger and 750 MHz for the advanced trigger, is used in these experiments. For signal averaging a 3-GHz microwave clock divider has been developed to synchronize the oscilloscope with the frequency of the EPR signal. Moreover, direct detection of continuous wave EPR signals at 2.5 GHz is described.     

Cover Picture

The cover picture shows the metalloporphyrin heterodimer [(tpp)Mo$\rm{\mathop{-}^{4}}$Re(oep)](+) with the novel [Mo$\rm{\mathop{-}^{4}}$Re](5+) core. The core represents the first example of a quadruple bond between elements of different triads, thus proving that heterometallic quadruple bonds are not limited to the Group 6 metals. From the space-filling model it is clear that there is no interaction between the stabilizing porphyrin ligands. The ORTEP plot in a projection along the Re-Mo axis emphasizes the perfectly eclipsed geometry of the porphyrins, which is unambiguous proof of the existence of the quadruple bond in the solid state. The diamagnetism and large magnetic anisotropy of the cation, as determined by (1)H NMR spectroscopy, indicate that the quadruple bond is retained in solution. A logical and well-defined synthetic route was used to synthesize the dimer, and can be extended to other metalloporphyrins to generate further novel quadruple bonds (the picture was generated by Marina Boulan, St. Petersburg, Russia), full details are reported by J. P. Collman et al. on p. 1271 ff.