Dichlorocarbene Addition to

In contrast to the terminal phosphinidene complex PhPW(CO)(5) (2), which adds to [5]metacyclophane (1) in a 1,4-fashion, dichlorocarbene preferentially adds in a 1,2-fashion to the formal "anti-Bredt" type double bond of the aromatic ring of 1 to afford the norcaradiene 11b, which immediately rearranges to the bridged cycloheptatriene 12b and further by a [1,5] sigmatropic chlorine migration to the isomeric 13b as the first observable product. More slowly, the latter isomerizes via a dissociative mechanism to give 15b. A computational study supports the notion that the [1,5] chlorine migration in the rearrangement 12b --> 13b, for which an activation barrier of 70.2 kJ mol(-)(1) was calculated, is essentially concerted with minor charge separation. In contrast, the analogous [1,5] chlorine migration in the flat model compound 7,7-dichlorocycloheptatriene (12a) displays features of a dissociative pathway.     

Bending of high energy beams using axial and planar channeling

A very strong and dramatic bending effect has been found for 12 GeV/c positive particles channeled along crystal axes and planes. For a combination of axial and planar channeling the bending efficiency is 5–10%. The maximum bending angle was 52 mrad obtained over a 20 mm long 〈111〉 Si-crystal. The axial channeling is also able to bend negative particles.     

Convergence to equilibrium in a system of reacting polymers

Chemical kinetics of a system of reacting polymers is modelled by an equation which shares certain properties with Boltzmann's equation. Being more tractable, however, this evolution may be of an illustrative value for the latter. The existence and uniqueness of solutions are analysed. We derive an entropy production inequality which is used to prove global exponential decay of the free energy. With its aid a uniform rate for strong convergence to equilibrium is proven. The generators of the linearlized flow at the vicinity of the equilibria are diagonalized.Work partly supported by U.S. National Science Foundation grant MCS 75-21684 A02     

Self-organizing neural networks for modeling robust 3D and 4D QSAR: application to dihydrofolate reductase inhibitors

We have used SOM and grid 3D and 4D QSAR schemes for modeling the activity of a series of dihydrofolate reductase inhibitors. Careful analysis of the performance and external predictivities proves that this method can provide an efficient inhibition model.     

Unified scaling law for earthquakes

We show that the distribution of waiting times between earthquakes occurring in California obeys a simple unified scaling law valid from tens of seconds to tens of years. The short time clustering, commonly referred to as aftershocks, is nothing but the short time limit of the general hierarchical properties of earthquakes. There is no unique operational way of distinguishing between main shocks and aftershocks. In the unified law, the Gutenberg-Richter b value, the exponent -1 of the Omori law for aftershocks, and the fractal dimension d(f) of earthquakes appear as critical indices.