Theoretical studies on reductive etherification reactions between aromatic aldehydes and alcohols

The mechanism of reductive etherification reactions between aromatic aldehydes and alcohols has been investigated with the DFT(B3LYP)/6-31G method. One or two BH(3) molecules have been used to simulate the role of the catalyst and reducing agent. The solvent effects of the title reactions have been studied by the PCM model. It is found that the reactions between aromatic aldehydes and primary, secondary, and tertiary alcohols can proceed more easily in a polar solvent such as acetonitrile. The results provide evidence in theory to broaden the applications of reductive etherification reactions for the optimization of the radiochemical synthesis process of (18)F-labeled ether radiotracers.     

Solvation largely accounts for the effect of N-alkylation on the properties of nickel(II/I) and chromium(III/II) cyclam complexes

The source of the effect of N-alkylation on the redox properties of Ni(II/I) and Cr(III/II) cyclam complexes has been investigated using DFT calculations. The structures of the anhydrous and hydrated complexes were optimized in the gas phase, and single point calculations were performed in a polarized continuum. The main results are the following: the decrease in outer sphere solvation upon N-alkylation is the major source of the relative stabilization of the lower oxidation state complexes by the tertiary amine ligands; tertiary amine nitrogen donors are stronger sigma-donors than the secondary amines, as predicted from the inductive effect of alkyls; steric strain elongates the metal-nitrogen bonds in the tertiary complexes and decreases the ligand strain energies; and the site of water binding to the complexes differs because of their different electronic structures (i.e., in the Ni complexes, the water molecules bind to the M[bond]N[bond]H sites, whereas in the Cr complexes they bind to the central metal cation). Outer sphere hydrogen bonding of water to the ligands in the coordination sphere lowers the ionization potentials by charge delocalization.     

Tachibana-type theorems and special Holonomy

Annals of Global Analysis and Geometry - In the present paper, we consider star-shaped mean convex hypersurfaces of the real, complex and quaternionic hyperbolic space evolving by a class of...     

Fractal wavelet dimensions and localization

In this paper we want to give a new definition of fractal dimensions as small scale behavior of theq-energy of wavelet transforms. This is a generalization of previous multi-fractal approaches. With this particular definition we will show that the 2-dimension (=correlation dimension) of the spectral measure determines the long time behavior of the time evolution generated by a bounded self-adjoint operator acting in some Hilbert space ?. It will be proved that for φ, ψ∈? we have $$\mathop {\lim \inf }\limits_{T \to \infty } \frac{{\log \int_0^T {d\omega \left| {\left\langle {\psi \left| {e^{ - iA\omega } } \right.\phi } \right\rangle } \right|^2 } }}{{\log T}} = - \kappa ^ + (2)$$ and that $$\mathop {\lim \sup }\limits_{T \to \infty } \frac{{\log \int_0^T {d\omega \left| {\left\langle {\psi \left| {e^{ - iA\omega } } \right.\phi } \right\rangle } \right|^2 } }}{{\log T}} = - \kappa ^ - (2),$$ wherek ^±(2) are the upper and lower correlation dimensions of the spectral measure associated with ψ and ?. A quantitative version of the RAGE theorem shall also be given.     

Development of a very low energy μ+ beam at PSI

At PSI we are investigating the technique of decelerating an existing very intense secondary beam of surface ⁺ (4 MeV) to an energy of 10 eV using appropriate moderators. These ⁺ can then be used as a source of a tertiary beam of low energy muons with tunable kinetic energy between 10 eV and 10 keV.With a 1000 A layer of solid Argon deposited on an Al substrate we obtain a moderation efficiency (with respect to the number of incoming surface ⁺) of the order of 10^–4.Results of our investigations and the present status of the project are presented together with future plans and possibilities.     

MC-simulation of the 3D,q=3 Potts model

We consider theq=3 Potts model in three dimensions by Monte Carlo simulations. The microcanonical density of states is calculated as a function of the internal energy of the system. We extrapolate the data for the simulated finite systems to the thermo-dynamic limit and find a discontinuous phase transition. This method is checked in the two-dimensional case, where exact results are known.     

Development of a beam of very slow polarized muons

During the last few decades, a variety of methods has been developed which makes use of polarized positive muons as a microscopic probe of the magnetic properties of condensed matter (muon spin rotation, relaxation, resonance,SR). Until now, available beams for SR studies have delivered 100% polarized muons with energies in the MeV range, resulting in a deep penetration of the muons into the sample material under investigation. This presently limits the applications of theSR technique to the study of the bulk characteristics of matter. To be able to control the implantation depth, a very low energy beam of polarized muons is being developed at the Paul Scherrer Institute. Very slow polarized muons (kinetic energy 10 eV, polarization 90%) are obtained from the moderation of a high energy muon beam in a thin film of an appropriate condensed gas. These muons can be used as a source for a beam of tunable energy between a few tens of eV and some tens of keV. Implantation depths in the range of few to a few hundreds of nanometers can thus be achieved by varying the energy.     

Jumps of Minimal Degrees Below 0'

We show that there is a degree a REA in and low over 0' suchthat no minimal degree below 0' jumps to a degree above a. Wealso show that every nonlow recursively enumerable degree boundsa nonlow minimal degree.     

On the complexity of the disjoint paths problem

In this paper we consider the disjoint paths problem. Given a graphG and a subsetS of the edge-set ofG the problem is to decide whether there exists a family of disjoint circuits inG each containing exactly one edge ofS such that every edge inS belongs to a circuit inC. By a well-known theorem of P. Seymour the edge-disjoint paths problem is polynomially solvable for Eulerian planar graphsG. We show that (assumingPNP) one can drop neither planarity nor the Eulerian condition onG without losing polynomial time solvability. We prove theNP-completeness of the planar edge-disjoint paths problem by showing theNP-completeness of the vertex disjoint paths problem for planar graphs with maximum vertex-degree three. This disproves (assumingPNP) a conjecture of A. Schrijver concerning the existence of a polynomial time algorithm for the planar vertex-disjoint paths problem. Furthermore we present a counterexample to a conjecture of A. Frank. This conjecture would have implied a polynomial algorithm for the planar edge-disjoint paths problem. Moreover we derive a complete characterization of all minorclosed classes of graphs for which the disjoint paths problem is polynomially solvable. Finally we show theNP-completeness of the half-integral relaxation of the edge-disjoint paths problem. This implies an answer to the long-standing question whether the edge-disjoint paths problem is polynomially solvable for Eulerian graphs.Supported by Sonderforschungsbereich 303 (DFG)